CN106164760A

CN106164760A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element

Info

Publication number: CN106164760A
Application number: CN201580017681.5A
Authority: CN
Inventors: 桧森章吾; 樱叶汀丹尼尔; 藤枝司; 后藤耕平; 芦泽亮; 芦泽亮一; 高桥真文
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2014-01-30
Filing date: 2015-01-30
Publication date: 2016-11-23
Anticipated expiration: 2035-01-30
Also published as: JPWO2015115588A1; TWI657297B; WO2015115588A1; CN106164760B; KR20160114645A; KR102357093B1; TW201541163A

Abstract

The present invention provides the aligning agent for liquid crystal of the polymerizable compound being improved containing the dissolubility in aligning agent for liquid crystal and the dissolubility in liquid crystal, and the storage stability of this aligning agent for liquid crystal is improved.The invention discloses a kind of aligning agent for liquid crystal, it contains: and [I] at least a kind of polymerizable compound in the group being made up of the compound shown in following formula I 1～I 3 (in formula, Ar₁～Ar₃It is each independently the divalent organic group of the aromatic ring comprising to have at least 1 halogenic substituent, n₁、n₂And n₆Represent the integer of 0～6, n independently of one another₃、n₄And n₅Represent the integer of 1～6, R independently of one another₁～R₃Represent the straight chained alkyl of hydrogen or carbon number 1～4 or the branched alkyl of carbon number 1～4 independently of one another)；And, [II] is selected from least a kind of polymer in polyimide precursor and polyimides.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element

Technical field

The present invention relates to can be used in manufacturing made by irradiation ultraviolet radiation in the state of applying voltage to liquid crystal molecule The liquid crystal made represent element aligning agent for liquid crystal, there is this aligning agent for liquid crystal and formed liquid crystal orientation film, there is this liquid crystal take Represent element to the liquid crystal of film.

Background technology

Make to carry out, relative to substrate, the mode that electric field responds by vertical orientated liquid crystal molecule (also referred to as vertical orientated (VA) mode) liquid crystal represent in element, in its manufacture process, irradiate on one side purple including apply voltage to liquid crystal molecule The operation of outside line.

For the liquid crystal of this vertical orientation mode represents element, it is known that following technology: in advance to liquid-crystal composition Middle interpolation photopolymerizable compound, used along with the vertical alignment layer of polyimides etc., voltage is applied to liquid crystal cells Irradiation ultraviolet radiation on one side, thus (PSA is (poly-to accelerate the response speed (referring for example to patent document 1 and non-patent literature 1) of liquid crystal Compound stable orientations, Polymer sustained Alignment) type liquid crystal display).

Generally, the incline direction of the liquid crystal molecule being responded electric field is used by projection, the expression arranging on substrate The slit etc. arranging in electrode controls, and it is said by adding photopolymerizable compound in liquid-crystal composition, to liquid crystal Unit applying voltage irradiation ultraviolet radiation on one side, thus what the incline direction defining liquid crystal molecule on liquid crystal orientation film was remembered Polymer architecture thing, therefore, compared with the method for incline direction only being controlled liquid crystal molecule by projection, slit, liquid crystal watch Show that the response speed of element accelerates.

In addition, report: by photopolymerizable compound being added in liquid crystal orientation film, rather than add to liquid crystal combination In thing, liquid crystal represents that the response speed of element also can accelerate (SC-PVA type liquid crystal display) (referring for example to non-patent literature 2).

Prior art literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2003-307720 publication.

Non-patent literature

Non-patent literature 1:K.Hanaoka, SID 04DIGEST, P.1200-1202.

Non-patent literature 2:K.H Y.-J.Lee, SID 09DIGEST, P.666-668.

Content of the invention

Problems to be solved by the invention

However, it is expected that further speed up the response speed that liquid crystal represents element.Herein, it may be considered that by increasing photopolymerization The addition of property compound accelerates the response speed that liquid crystal represents element, but existing photopolymerizable compound possess be difficult to molten The solvent of use in aligning agent for liquid crystal, the character of liquid crystal.Therefore, when preserving aligning agent for liquid crystal, this optical polymerism chemical combination is produced The problem that thing separates out this storage stability.In addition, liquid crystal represent element in its manufacturing process bearing temperature change when, sometimes A part of polymerizable compound from liquid crystal orientation film dissolution in liquid crystal or crystallize in liquid crystal further.Especially It is, it is believed that: when dissolubility in liquid crystal for the polymerizable compound is low, easily crystallize in liquid crystal.This polymerization Property crystallization in liquid crystal for the compound can become the bright spot source representing in element, cause the expression quality of element to reduce.Enter And, impurity can be become during undissolved photopolymerizable compound residual, it is possible to become the reliability fall making liquid crystal represent element The reason that low.For example, liquid crystal represent element be possible to produce ghost, after image and cause represent quality reduce.

It is an object of the invention to solve above-mentioned problem of the prior art point.

Specifically, it is an object of the invention to, provide containing the dissolubility in aligning agent for liquid crystal with in liquid crystal The aligning agent for liquid crystal of the polymerizable compound that dissolubility is improved, it is stable that this aligning agent for liquid crystal has the preservation being improved Property.

In addition, it is an object of the invention to, the liquid crystal orientation film having this aligning agent for liquid crystal and being formed is provided, there is this liquid The liquid crystal of brilliant alignment films represents element.

For solution to problem

The present inventor etc. are found that following technical scheme.

<1>a kind of aligning agent for liquid crystal, it contains:

[I] at least a kind of polymerizable compound in the group being made up of the compound shown in following formula I-1～I-3； And

[II] is selected from least a kind of polymer in polyimide precursor and polyimides.

(in formula, Ar₁～Ar₃The divalence being each independently the aromatic ring comprising to have at least 1 halogenic substituent has Machine group, n₁、n₂And n₆Represent the integer of 0～6, n independently of one another₃、n₄And n₅Represent the integer of 1～6, R independently of one another₁~ R₃Represent the straight chained alkyl of hydrogen or carbon number 1～4 or the branched alkyl of carbon number 1～4 independently of one another)

<2>in above-mentioned<1>, Ar₁～Ar₃Can be each independently in the group being made up of following formula IB-1～IB-3 Divalent organic group (in formula, X represents halogen group, m₁～m₈It is each independently integer, m₁+m₂It is more than 1 and less than 8, m₃ +m₄+m₅It is more than 1 and less than 10, m₆+m₇+m₈It is more than 1 and less than 12).

<3>, in above-mentioned<2>, the group shown in Formulas I B-1 can be represented by following formula IB-1a, the base shown in previously described formula IB-2 Group can be represented by following formula IB-2a, and the group shown in previously described formula IB-3 can be represented by following formula IB-3a.

<4>, in any one of above-mentioned<1>～<3>, [II] polymer can have the side chain that (I) makes liquid crystal vertical-tropism.

<5>, in above-mentioned<4>, [II] polymer can also have (II) photoreactive side chain.

<6>a kind of liquid crystal orientation film, it is the aligning agent for liquid crystal having any one of above-mentioned<1>～<5>and is formed.

<7>a kind of liquid crystal represents element, and it has the liquid crystal orientation film of above-mentioned<6>.

The effect of invention

Carried by means of the invention it is possible to provide containing the dissolubility in aligning agent for liquid crystal and the dissolubility in liquid crystal The aligning agent for liquid crystal of high polymerizable compound, this aligning agent for liquid crystal has the storage stability being improved.

In addition, by means of the invention it is possible to provide the liquid crystal orientation film that there is this aligning agent for liquid crystal and formed, there is this liquid crystal The liquid crystal of alignment films represents element.

Detailed description of the invention

Hereinafter, the technical scheme that the application records is described in detail.

The application provides the polymerization being improved containing the dissolubility in aligning agent for liquid crystal and the dissolubility in liquid crystal The aligning agent for liquid crystal of property compound.

In addition, the application provides the liquid crystal orientation film having this aligning agent for liquid crystal and being formed, has this liquid crystal orientation film Liquid crystal represents element.

Hereinafter, successively illustrate aligning agent for liquid crystal, there is this aligning agent for liquid crystal and formed liquid crystal orientation film, there is this liquid crystal The liquid crystal of alignment films represents element.

The aligning agent for liquid crystal of the application contains: [I] is selected from the group being made up of the compound shown in following formula I-1～I-3 In at least a kind of polymerizable compound；And [II] is selected from least a kind of polymer in polyimide precursor and polyimides.

In formula I-1～I-3, Ar₁～Ar₃It is each independently the aromatic ring comprising that there is at least 1 halogenic substituent Divalent organic group, n₁、n₂And n₆Represent the integer of 0～6, n independently of one another₃、n₄And n₅Represent 1～6 independently of one another Integer, R₁～R₃Represent the straight chained alkyl of hydrogen or carbon number 1～4 or the branched alkyl of carbon number 1～4 independently of one another.

" [I] polymerizable compound "

The aligning agent for liquid crystal of the application contains [I] in the group being made up of the compound shown in above-mentioned formula I-1～I-3 At least a kind of polymerizable compound.

The Ar of formula I-1～I-3₁～Ar₃Can be each independently in the group being made up of following formula IB-1～IB-3 Divalent group (in formula, X represents halogen group, m₁～m₈It is each independently integer, m₁+m₂Be more than 1 and less than 8, preferably It is more than 1 and less than 4, m₃+m₄+m₅It is more than 1 and less than 10, be preferably more than 1 and less than 6 and m₄+m₅It is less than 2, m₆+m₇ +m₈It is more than 1 and less than 12, is preferably more than 1 and less than 4).

In the aligning agent for liquid crystal of the application, polymerizable compound can be a kind, can be multiple as required.

The amount of polymerizable compound can be 1～30 mass % relative to the solid constituent in aligning agent for liquid crystal, be preferably 3 ～20 mass %, more preferably 5～15 mass %.

As the divalent group shown in Formulas I B-1～IB-3, specifically, the group shown in following formula can be listed, but not It is defined in this.

As the divalent group shown in Formulas I B-1～IB-3, it can be following group.That is, the group shown in Formulas I B-1 is permissible Group shown in following formula IB-1a, the group shown in Formulas I B-2 can group shown in following formula IB-2a, Formulas I B-3 institute The group showing can group shown in following formula IB-3a.

<[II] is selected from least a kind of polymer in polyimide precursor and polyimides>

At least a kind of polymer that [II] is selected from polyimide precursor and polyimides can use in aligning agent for liquid crystal Use existing known or known polyimide precursor or polyimides may be become future.It should be noted that polyamides is sub- Amine precursor specifically refers to comprise the meaning of polyamic acid and poly amic acid ester.

When [II] polyimide precursor or polyimides are for PSA type liquid crystal display, can have (I) makes liquid crystal vertical The side chain of orientation.

The side chain of liquid crystal vertical-tropism " (I) make "

(I) side chain (hereinafter also referred to side chain A) making liquid crystal vertical-tropism refers to possess and makes liquid crystal molecule relative to substrate Carrying out the side chain of vertical orientated ability, then its structure not being limited as long as having this ability.As this side chain, such as Know is that the alkyl of long-chain and/or fluoroalkyl, end have the cyclic group of alkyl and/or fluoroalkyl, steroid radical etc., it is possible to suitable For the present invention.As long as these groups possess aforementioned capabilities, then can be bonded directly to polyimide precursor or polyimides Main chain, it is also possible to be bonded by suitable linking group.

Above-mentioned side chain A for example can exemplify the side chain shown in following formula (a).

It should be noted that in formula (a), l, m and n represent the integer of 0 or 1, R independently of one another¹Represent carbon number 2～ Alkylidene-the ether of the alkylidene of 6 ,-O-,-COO-,-OCO-,-NHCO-,-CONH-or carbon number 1～3, R²、R³With R⁴Represent phenylene or ring alkylidene, R independently of one another⁵Represent hydrogen atom, the alkyl of carbon number 2～24 or fluorine-containing alkyl, virtue Fragrant ring, aliphatic ring, heterocycle or the big ring-type replacement body being formed by them.

R in formula (a)¹Represent the alkylidene of carbon number 2～6 ,-O-,-COO-,-OCO-,-NHCO-,-CONH-or Alkylidene-the ether of person's carbon number 1～3.Wherein, from synthesis easiness from the viewpoint of, be preferably-O-,-COO-,- CONH-, the alkylidene-ether of carbon number 1～3.

R in formula (a)²、R³And R⁴Represent phenylene or ring alkylidene independently of one another.From synthesis easiness and make liquid crystal From the viewpoint of vertical orientated ability, l, m, n, the R shown in preferably following table²、R³With R⁴Combination.

[table 1]

R in formula (a)⁵The alkyl of expression hydrogen atom or carbon number 2～24 or fluorine-containing alkyl, aromatic rings, aliphatic Ring, heterocycle or the big ring-type replacement body being formed by them.When at least one in l, m, n is 1, as R⁵Structure, preferably Alkane for the alkyl of hydrogen atom or carbon number 2～14 or fluorine-containing alkyl, more preferably hydrogen atom or carbon number 2～12 Base or fluorine-containing alkyl.

During in addition, l, m, n are 0, as R⁵Structure, preferably the alkyl of carbon number 12～22 or fluorine-containing alkyl, Aromatic rings, aliphatic ring, heterocycle or big ring-type the replacement body, the more preferably alkane of carbon number 12～20 that are formed by them Base or fluorine-containing alkyl.

The ability making liquid crystal vertical-tropism is different because of the structure of above-mentioned side chain A, in general, and the side chain that contains in polymer When the quantitative change of A is many, making the ability of liquid crystal vertical-tropism improve, when quantitative change is few, ability declines.In addition, the side chain containing circulus A is compared with the side chain A of chain alkyl, even if content there is also the tendency making liquid crystal vertical-tropism less.

As the amount of the side chain A in the polyimide precursor using in the present invention or polyimides, as long as aforementioned Liquid crystal orientation film can make the scope of liquid crystal vertical-tropism just be not particularly limited.Wherein, possessing foregoing liquid crystal alignment films Liquid crystal represents in element, it is desirable to when further speeding up the response speed of liquid crystal, within can keeping vertical orientated scope, and side chain The amount of A is few preferably as far as possible.

When [II] polyimide precursor or polyimides are for SC-PVA type liquid crystal display, liquid can be made at above-mentioned (I) On the basis of brilliant vertical orientated side chain, also there is (II) photoreactive side chain.

<(II) photoreactive side chain>

Photoreactive side chain (hereinafter also referred to side chain B) is referred to have and is irradiated by ultraviolet and react it is thus possible to shape Become the bridging property side chain of functional group's (hereinafter also referred to photo-crosslinking group) of covalent bond or have and irradiated by ultraviolet and produce The side chain of the generation optical free radical of the functional group of raw free radical, does not limit as long as having this ability then its structure.

Among this side chain, such as it is known that contain vinyl, acryloyl group, methylacryloyl, anthryl, cinnamoyl Base, chalcone base, cumarin base, dimaleoyl imino, stilbene radicals etc. are as the side chain etc. of photo-crosslinking group, it is also possible to be applicable to this Invention.Irradiated by ultraviolet furthermore it is also possible to compatibly use and produce the ad hoc structure of free radical.As long as these groups have Standby aforementioned capabilities, then can be bonded directly to the main chain of polyimide precursor or polyimides, it is also possible to by suitable connection Group is bonded.

Above-mentioned side chain B for example can exemplify the side chain shown in following formula (b-1)～(b-3).It should be noted that formula (b- 2) side chain shown in possesses the structure with cinnamoyl and methylacryloyl, and the side chain shown in formula (b-3) possesses by purple Outside line is irradiated and is produced the structure of free radical.In formula, for Ar₄、Q、R⁶～R¹⁷、S、T₁、T₂, as described later.

In formula (b-1), R⁶Expression-CH₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、-N (CH₃)-、-CON(CH₃)-、-N(CH₃) any one in CO-；R⁷Represent carbon number 1 that is ring-type, unsubstituted or that be replaced by fluorine atoms The alkylidene of～carbon number 20, herein, any-CH in alkylidene₂-optionally by-CF₂-or-CH=CH-displacement, it is being exemplified below Any group not adjacent to each other in the case of, be optionally replaced as these group :-O-,-COO-,-OCO-,-NHCO-,- CONH-,-NH-, carbocyclic ring, heterocycle.R⁸Expression-CH₂-、-O-、-COO-、-OCO-、-NHCO-、-NH-、-N(CH₃)-、-CON (CH₃)-、-N(CH₃) CO-, any one in carbocyclic ring or heterocycle；R⁹Represent ethenylphenyl ,-CR¹⁰=CH₂Base, carbocyclic ring, heterocycle Or the structure shown in below formula R9-1～R9-34；R¹⁰Represent hydrogen atom or the methyl being optionally replaced by fluorine atoms.

In formula (b-1), R⁶For selected from-CH₂-、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、- OCO-、-CON(CH₃)-and-N (CH₃) linking group in CO-.These linking groups can be come by common methodology of organic synthesis Formed, from the viewpoint of synthesis easiness, be preferably-CH₂-、-O-、-COO-、-NHCO-、-NH-、-CH₂O-。

In formula (b-1), R⁷Represent the alkylidene of carbon number 1～carbon number 20 that is ring-type, unsubstituted or that be replaced by fluorine atoms, this Place, any-CH in alkylidene₂-optionally by-CF₂-or-CH=CH-displacement, in any group being exemplified below out not phase each other It in the case of adjacent, is optionally replaced as these group :-O-,-COO-,-NHCO-,-NH-, carbocyclic ring, heterocycle.

As carbocyclic ring, heterocycle, specifically, following such structure can be listed, but be not limited to this.

In formula (b-1), R⁸For selected from-CH₂-、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、- OCO-、-CON(CH₃)-、-N(CH₃) CO-, the linking group in carbocyclic ring and heterocycle.Wherein, from the viewpoint of synthesis easness, It is preferably-CH₂-,-O-,-COO-,-OCO-, NHCO-,-NH-, carbocyclic ring or heterocycle.As the concrete example of carbocyclic ring and heterocycle, as above Shown in.

In formula (b-1), R⁹Represent styryl ,-CR¹⁰=CH₂, carbocyclic ring, shown in heterocycle or above-mentioned formula R9-1～R9-31 Structure, R¹⁰Represent hydrogen atom or the methyl being optionally replaced by fluorine atoms.

Wherein, from the viewpoint of photoreactivity, R⁹More preferably styryl ,-CH=CH₂、-C(CH₃)=CH₂On or State formula R9-2, R9-12 or R9-15.

-R¹⁰-R¹¹-R¹²-R¹³-R¹⁴-R¹⁵ (b-2)

In formula (b-2), R¹⁰Represent and be selected from-CH₂-, in-O-,-CONH-,-NHCO-,-COO-,-OCO-,-NH-,-CO- Group.

R¹¹For the alkylidene, the carbocyclic ring of divalence or the heterocycle that are formed by carbon number 1～carbon number 30, this alkylidene, the carbocyclic ring of divalence Or one or more hydrogen atoms in heterocycle are optionally replaced by fluorine atom or organic group.In addition, at any base being exemplified below out In the case that group is not adjacent to each other, R¹¹In-CH₂-be optionally replaced as these group :-O-,-NHCO-,-CONH-,-COO-,- OCO-、-NH-、-NHCONH-、-CO-。

R¹²Expression-CH₂-,-O-,-CONH-,-NHCO-,-COO-,-OCO-,-NH-,-CO-, any one in singly-bound.

R¹³Represent the photocrosslinking reaction groups such as cinnamoyl, chalcone base, cumarin base.

R¹⁴Alkylidene, the carbocyclic ring of divalence or the heterocycle formed for singly-bound or by carbon number 1～carbon number 30, this alkylidene, two One or more hydrogen atoms in the carbocyclic ring of valency or heterocycle are optionally replaced by fluorine atom or organic group.In addition, be exemplified below out Any group not adjacent to each other in the case of, R¹⁴In-CH₂-be optionally replaced as these group :-O-,-NHCO-,- CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。

R¹⁵Represent selected from acryloyl group, methylacryloyl any one in optical polymerism group.

Among side chain shown in formula (b-2), as-R¹³-R¹⁴-R¹⁵The concrete example of shown group, can list following that The structure of sample, but it is not limited to them.It should be noted that in following structure, R represents hydrogen atom or methyl.

In formula (b-3), Ar₄Representing the aromatic hydrocarbyl in phenylene, naphthylene, biphenylene, they are upper optionally Being replaced with organic group, hydrogen atom is optionally substituted with halogen atoms.

R₁₆And R₁₇It is each independently alkyl, alkoxyl or benzyl, the phenethyl of carbon number 1～10, be alkyl, alkane During epoxide, R can be used₁₆、R₁₇Form ring.

T₁And T₂Represent independently of one another singly-bound or-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-,- CH₂O-、-N(CH₃)-、-CON(CH₃)-or-N (CH₃) linking group of CO-.

S represents singly-bound or alkylidene (wherein, the alkylidene of carbon number 1～20 that is unsubstituted or that be replaced by fluorine atoms In-CH₂-or-CF₂-optionally arbitrarily replaced by-CH=CH-, in the situation that any group being exemplified below out is not adjacent to each other Under, it is optionally replaced as these group :-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-, divalence carbocyclic ring, bivalent heterocyclic.).

Q represents that (in formula, R represents hydrogen atom or the alkyl of carbon number 1～4, R to following formula₃Expression-CH₂-、-NR-、- O-,-S-) shown in structure.

Among side chain shown in formula (b-3), as-Ar₄-CO-CQR¹⁶R¹⁷The concrete example of shown group, can list with Lower such structure, but it is not limited to them.

As long as the amount of side chain B can accelerate the scope that liquid crystal represents the liquid crystal response speed in element, just do not have It is particularly limited to.When wanting to further speed up the liquid crystal response speed that liquid crystal represents in element, in the scope not affecting other characteristics In, many preferably as far as possible.

As described above, polyimide precursor refers to comprise the meaning of polyamic acid and poly amic acid ester.Hereinafter, especially pin Polyamic acid is described in detail, for poly amic acid ester, it is also possible to by existing known method or with aftermentioned polyamic acid Prepared by same or similar method.

The polyamic acid with side chain A can be obtained as below: by making among as the diamines of raw material and tetracarboxylic anhydride Any one has side chain A or both have side chain A, makes this raw material react thus obtains.Wherein, from the appearance of Material synthesis Yi Xing etc. set out, it is preferable to use have the method for the diamine compound of side chain A.

The polyamic acid with side chain A and side chain B can be obtained as below: by making the diamines as raw material and tetracarboxylic anhydride Among only any one have side chain A and side chain B or any one only there is side chain A and another one only have side chain B or Any one has side chain A and side chain B and another one has side chain A or any one has side chain A and side chain B and another one tool Have side chain B or both there is side chain A and side chain B, make this raw material react thus obtain.Wherein, from the appearance of Material synthesis Yi Xing etc. set out, it is preferable to use diamine compound, the diamine compound with side chain B with side chain A and do not have side The method of the tetrabasic carboxylic acid of chain A or side chain B.

Hereinafter, illustrate for the diamine compound with side chain A, then, for the diamine compound with side chain B Illustrate.

As the diamine compound (hereinafter also referred to diamines A) with side chain A, two amine side chain tools can be listed as an example There is the diamines of alkyl, fluorine-containing alkyl, aromatic rings, aliphatic ring, heterocycle or the big ring-type replacement body being formed by them.Specifically For, the diamines with side chain shown in previously described formula (a) can be listed.More specifically, can list such as following formula (1), (3), the diamines shown in (4), (5), but it is not limited to this.It should be noted that for l, m, n, R in formula (1)¹～R⁵Determine Justice is identical with previously described formula (a).

In formula (3) or formula (4), A₁₀Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH independently of one another₂-、-O-、- CO-or-NH-, A₁₁Representing singly-bound or phenylene, a represents side chain A, and a ' represents by selected from alkyl, fluorine-containing alkyl, aromatic rings, fat The big ring-type replacement body that the combination of the arbitrary structures in race's ring, heterocycle is formed.

In formula (5), A₁₄The alkyl of the carbon number 3～20 for being optionally replaced by fluorine atoms, A₁₅For 1,4-cyclohexylene or 1,4- Phenylene, A₁₆It is oxygen atom or-COO-* (wherein, indicates key and the A of " * "₃It is bonded), A₁₇For oxygen atom or-COO-* (its In, indicate key and the (CH of " * "₂)a₂It is bonded.).In addition, a₁It is the integer of 0 or 1, a₂It is the integer of 2～10, a₃It is 0 or 1 Integer.)

Two amino (-NH in formula (1)₂) bonding position do not limit.Specifically, the linker relative to side chain Group, can list 2 on phenyl ring, the position of 3, the position of 2,4,2,5 position, 2,6 position, 3,4 position, the position of 3,5 Put.Wherein, from the viewpoint of reactivity when synthesizing polyamides acid, the position of preferably 2,4, the position or 3 of 2,5, the position of 5 Put.In view of synthesis diamine compound when easiness when, more preferably 2, the position of 4 or 3, the position of 5.

As the concrete structure of formula (1), the diamines shown in following formula [A-1]～formula [A-24] can be exemplified, but do not limit In this.

In formula [A-1]～formula [A-5], A₁It is each independently the alkyl of carbon number more than 2 and less than 24 or fluorine-containing alkyl.

In formula [A-6] and formula [A-7], A₂Represent-O-,-OCH independently of one another₂-、-CH₂O-、-COOCH₂-or- CH₂OCO-, A₃It is each independently alkyl, alkoxyl, fluorine-containing alkyl or the fluoroalkoxy of carbon number more than 1 and less than 22.

In formula [A-8]～formula [A-10], A₄Independently of one another represent-COO-,-OCO-,-CONH-,-NHCO-,- COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-or-CH₂-, A₅It is each independently alkyl, the alkane of carbon number more than 1 and less than 22 Epoxide, fluorine-containing alkyl or fluoroalkoxy.

In formula [A-11] and formula [A-12], A₆Independently of one another represent-COO-,-OCO-,-CONH-,-NHCO-,- COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-,-O-or-NH-, A₇For fluorine-based, cyano group, fluoroform alkyl, nitro, idol Nitrogen base, formoxyl, acetyl group, acetoxyl group or hydroxyl.

In formula [A-13] and formula [A-14], A₈It is each independently the alkyl of carbon number more than 3 and less than 12, Isosorbide-5-Nitrae-cycloethylene The cis-trans isomerization of base is respectively transisomer.

In formula [A-15] and formula [A-16], A₉It is each independently the alkyl of carbon number more than 3 and less than 12, Isosorbide-5-Nitrae-cycloethylene The cis-trans isomerization of base is respectively transisomer.

As the concrete example of the diamines shown in formula (3), following formula [A-25]～formula [A-30] (A can be listed₁₂Represent- COO-、-OCO-、-CONH-、-NHCO-、-CH₂-,-O-,-CO-or-NH-, A₁₃Represent carbon number more than 1 and less than 22 alkyl or Fluorine-containing alkyl.Diamines shown in), but it is not limited to this.

As the concrete example of the diamines shown in formula (4), the diamines shown in following formula [A-31]～formula [A-32] can be listed, But it is not limited to this.

Wherein, from the viewpoint of making the ability of liquid crystal vertical-tropism, liquid crystal response speed, be preferably [A-1], [A-2], The diamines of [A-3], [A-7], [A-14], [A-16], [A-21] and [A-22].

Above-mentioned diamine compound also can keep according to liquid crystal aligning when making liquid crystal orientation film, tilt angle, voltage The characteristic such as characteristic, accumulated charge and use a kind or be mixed with two or more.

Among the 100 moles of % of diamine component using to synthesize the polyamic acid with side chain A, diamines A can be 5-70 mole of %, preferably 10-50 mole %, more preferably 20-50 mole of %.

As the example of the diamine compound (hereinafter also referred to diamines B) with side chain B, two amine side chains can be listed and have Vinyl, acryloyl group, methylacryloyl, anthryl, cinnamoyl, chalcone base, cumarin base, dimaleoyl imino, stilbene The diamines of the photo-crosslinking groups such as base；Have and irradiated by ultraviolet and produce the diamines of the ad hoc structure of free radical.Specifically, The diamines with side chain shown in previously described formula (b-1)～(b-3) can be listed.As concrete example, following formula (2) can be listed (the R in formula (2)⁶、R⁷、R⁸、R⁹And R¹⁰Definition and previously described formula (b-1) identical) shown in diamines, but be not limited to this.

Two amino (-NH in formula (2)₂) bonding position do not limit.Specifically, the linker relative to side chain Group, can list 2 on phenyl ring, the position of 3, the position of 2,4,2,5 position, 2,6 position, 3,4 position, the position of 3,5 Put.Wherein, from the viewpoint of reactivity when synthesizing polyamides acid, the position of preferably 2,4, the position or 3 of 2,5, the position of 5 Put.In view of synthesis diamine compound when easiness when, more preferably 2, the position of 4 or 3, the position of 5.

Specifically, following such compound can be listed, but be not limited to this.It should be noted that following chemical combination In thing, X represents the linking group in the group of singly-bound, ether, benzyl oxide, ester, acid amides and amino composition independently, and R represents that hydrogen is former Son or methyl, S₁Represent singly-bound or the alkylidene of carbon number 1～20 that is unsubstituted or that be replaced by fluorine atoms.In addition, l, m and N represents the integer of 0～20 independently of one another.

Above-mentioned diamine compound also can be protected according to liquid crystal aligning when making liquid crystal orientation film, tilt angle, voltage Hold the characteristic such as characteristic, accumulated charge, make liquid crystal response speed when liquid crystal represents element etc. and use a kind or be used in mixed way Two or more.

Among the 100 moles of % of diamine component using for synthesizing polyamides acid, diamines B can be more than 0% and 95 It mole below %, is preferably 20-80 mole of %, more preferably 40-70 mole of %.

Polyamic acid used in the present invention can be applied in combination in the range of not damaging effect of the present invention except diamines A and Other diamine compounds beyond diamines B combine as diamine component.It is exemplified below out its concrete example.

Have: p-phenylenediamine, 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene diamine (MPD), 2,4-bis- Methylresorcinol diamines, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5- Diaminophenol, 3,5-diaminourea benzyl alcohol, 2,4-diaminourea benzyl alcohol, 4,6-diamino resorcin, 4,4 '-diaminourea connection Benzene, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4, 4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl- 4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-diaminourea connection Benzene, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-two Aminodiphenylmethane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3, 4 '-diaminodiphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, 4,4 '-sulfonyldianiline, 3,3 '-sulphur Acyl group diphenylamines, double (4-aminophenyl) silane, double (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, two Methyl-bis-(3-aminophenyl) silane, 4,4 '-phenothiazine, 3,3 '-phenothiazine, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyl amine, 2,3 '-diamino-diphenyl Amine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diaminourea Diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminourea Benzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 '-diaminourea hexichol Ketone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, Double (4-aminophenyl) ethane of 2,5-diaminonaphthalene, 2,6 diaminonaphthalenes, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-, 1, Double (3-aminophenyl) ethane of 2-, double (4-aminophenyl) propane of 1,3-, double (3-aminophenyl) propane of 1,3-, double (4 ammonia of 1,4- Base phenyl) butane, double (3-aminophenyl) butane of 1,4-, double (3,5-diethyl-4-aminophenyl) methane, double (the 4-ammonia of 1,4- Phenoxyl) benzene, double (4-amino-benzene oxygen) benzene of 1,3-, double (4-aminophenyl) benzene of 1,4-, double (4-aminophenyl) benzene of 1,3-, Double (4-aminobenzyl) benzene of 1,4-, double (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[1,4-phenylene is double (methylene)] hexichol Amine, 4,4 '-[1,3-phenylene double (methylene)] diphenylamines, 3,4 '-[1,4-phenylene is double (methylene)] diphenylamines, 3,4 '- [1,3-phenylene is double (methylene)] diphenylamines, 3,3 '-[1,4-phenylene is double (methylene)] diphenylamines, 3,3 '-[the sub-benzene of 1,3- Base double (methylene)] diphenylamines, 1,4-phenylene double [(4-aminophenyl) ketone], 1,4-phenylene be double [(3-aminophenyl) Ketone], 1,3-phenylene double [(4-aminophenyl) ketone], 1,3-phenylene double [(3-aminophenyl) ketone], the sub-benzene of 1,4- Base double (PABA ester), 1,4-phenylene double (3-Aminobenzoate), the double (PABA of 1,3-phenylene Ester), 1,3-phenylene double (3-Aminobenzoate), double (4-aminophenyl) terephthalate, double (3-aminophenyls) right Phthalic acid ester, double (4-aminophenyl) isophthalic acid ester, double (3-aminophenyl) isophthalic acid ester, N, N '-(1,4-is sub- Phenyl) double (4-aminobenzamides), N, N '-(1,3-phenylene) double (4-aminobenzamide), N, N '-(1,4-phenylene) Double (3-ABs), N, N '-(1,3-phenylene) double (3-AB), N, N '-bis-(4-aminophenyl) is right Benzenedicarboxamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, 9,10-double (4-aminophenyl) anthracene, 4,4 '-bis-(4-amino-benzene oxygen) hexichol Base sulfone, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 2,2 '-bis-(4-aminophenyl) HFC-236fas, 2,2 '-bis-(3-aminophenyl) HFC-236fas, 2,2 '-bis-(3-amino-4-methyl Phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino- 4-aminomethyl phenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, double (4-amino-benzene oxygen) methane, 1,2-be double Double (4-amino-benzene oxygen) propane of (4-amino-benzene oxygen) ethane, 1,3-, double (3-amino-benzene oxygen) propane of 1,3-, 1,4-are double Double (3-amino-benzene oxygen) butane of (4-amino-benzene oxygen) butane, 1,4-, double (4-amino-benzene oxygen) pentane of 1,5-, 1,5-are double Double (4-amino-benzene oxygen) hexane of (3-amino-benzene oxygen) pentane, 1,6-, double (3-amino-benzene oxygen) hexane of 1,6-, 1,7-are double Double (3-amino-benzene oxygen) heptane of (4-amino-benzene oxygen) heptane, 1,7-, double (4-amino-benzene oxygen) octane of 1,8-, 1,8-are double Double (4-amino-benzene oxygen) nonane of (3-amino-benzene oxygen) octane, 1,9-, double (3-amino-benzene oxygen) nonane of 1,9-, 1,10-are double Double (4-amino-benzene oxygen) hendecane of double (3-amino-benzene oxygen) decane of (4-amino-benzene oxygen) decane, 1,10-, 1,11-, 1, Double (3-amino-benzene oxygen) hendecane of 11-, double (4-amino-benzene oxygen) dodecane of 1,12-, double (the 3-amino-benzene oxygen) ten of 1,12- The ester ring types two such as the aromatic diamines such as dioxane, double (4-aminocyclohexyl) methane, double (4-amino-3-methylcyclohexyl) methane Amine, 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminourea heptan Alkane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, 1,12-diamino The aliphatic diamines such as base dodecane.

Other diamine compound above-mentioned also can be according to liquid crystal aligning when making liquid crystal orientation film, tilt angle, electricity The characteristic such as retention performance, accumulated charge is pressed to use a kind or be mixed with two or more.

In the synthesis of polyamic acid used in the present invention, the tetracarboxylic dianhydride reacting with above-mentioned diamine component does not has It is particularly limited to.It is exemplified below out its concrete example.

Can list by pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid Acid, 2,3,6,7-anthracene tetrabasic carboxylic acid, 1,2,5,6-anthracene tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyl tetracarboxylic acid Sour, double (3,4-dicarboxyphenyi) ether, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, double (3,4-dicarboxyphenyi) sulfone, double (3,4- Dicarboxyphenyi) methane, double (3,4-dicarboxyphenyi) propane of 2,2-, double (the 3,4-dicarboxyl of 1,1,1,3,3,3-hexafluoro-2,2- Phenyl) propane, double (3,4-dicarboxyphenyi) dimethylsilane, double (3,4-dicarboxyphenyi) diphenyl silane, 2,3,4,5- Pyridine tetrabasic carboxylic acid, 2,6-double (3,4-dicarboxyphenyi) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid, 3,4,9,10-tetra- Adjacent benzene tetracarboxylic acid (the oxy-diphthalic of carboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid, oxo two Tetracarboxylic acid), 1,2,3,4-cyclobutane tetrabasic carboxylic acid, 1,2,3,4-pentamethylene tetrabasic carboxylic acid, 1,2,4,5-hexamethylene Alkane tetrabasic carboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid, 1,2,3,4-cycloheptane tetrabasic carboxylic acid, 2,3,4,5-oxolane tetrabasic carboxylic acid, 3,4-dicarboxyl-1-cyclohexyl butanedioic acid, 2,3,5-tricarboxylic cyclopentyl acetic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene Butanedioic acid, bicyclic [3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid, bicyclic [4,3,0] nonane-2,4,7,9-tetrabasic carboxylic acid, bicyclic [4, 4,0] decane-2,4,7,9-tetrabasic carboxylic acid, bicyclic [4,4,0] decane-2,4,8,10-tetrabasic carboxylic acid, three rings [6.3.0.0<2,6>] ten One alkane-3,5,9,11-tetrabasic carboxylic acid, 1,2,3,4-BTCA, 4-(2,5-dioxotetrahydrol furans-3-base)-1,2,3,4- Naphthane-1,2-dicarboxylic acids, bicyclic [2,2,2] octyl-7-alkene-2,3,5,6-tetrabasic carboxylic acid, 5-(2,5-dioxotetrahydrol furyl)- 3-methyl-3-hexamethylene-1,2-dicarboxylic acids, Fourth Ring [6,2,1,1,0,2,7] dodecane-4,5,9,10-tetrabasic carboxylic acid, 3,5,6-tri- The tetracarboxylic dianhydride that carboxyl norbornane-2:3,5:6 dicarboxylic acids, 1,2,4,5-cyclopentanetetracarboxylic etc. obtain.

Tetracarboxylic dianhydride can be according to liquid crystal aligning when making liquid crystal orientation film, voltage retention performance, accumulated charge etc. Characteristic and use a kind or be applied in combination two or more.

When obtaining polyamic acid by the reaction of diamine component and tetracarboxylic dianhydride, it is possible to use known synthesis side Method.It is said that in general, be the method making diamine component and tetracarboxylic dianhydride react in organic solvent.Diamine component and tetracarboxylic acid The reaction of acid dianhydride is easier to carry out in organic solvent, and will not produce accessory substance, is favourable from this point of view.

As the organic solvent using in above-mentioned reaction, as long as dissolve the solvent of generated polyamic acid, just do not have It is particularly limited to.And then, even the organic solvent of insoluble polyamic acid, in the scope that the polyamic acid being generated will not separate out In, it is also possible to mixing to above-mentioned solvent uses.It should be noted that the moisture in organic solvent can suppress polymerisation, enter And become the reason that make the polyamic acid of generation hydrolyze, therefore, organic solvent uses after preferably dehydrating.

Hereinafter, the concrete example of organic solvent is listed.

Have: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N-DEF, N-METHYLFORMAMIDE, N- N-methyl-2-2-pyrrolidone N, N-ethyl-2-pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-2-imidazolinone, 3-methoxyl group- N, N-dimethylpropionamide, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, Gamma-butyrolacton, isopropanol, methoxy amylalcohol, dipentene, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl Base ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, butyl cellosolve acetate, second Base cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, second Glycol monobutyl ether, propane diols, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, glycol tertiary butyl ether, dipropyl Glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethyl two Diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, DPG list acetic acid Ester list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, 3 third Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxane, n-hexane, pentane, normal octane, diethyl ether, hexamethylene Ketone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, the third two Alcohol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3- Methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, two Glyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol.These organic solvents can be used alone, it is also possible to It is used in mixed way.

When making diamine component and tetracarboxylic dianhydride's composition react in organic solvent, following method can be listed: stir Mix the solution making diamine component be dispersed or dissolved in organic solvent, directly add tetracarboxylic dianhydride's composition or make it disperse Or it is dissolved in organic solvent the method added；Otherwise, form to making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent Solution in add diamine component method；Alternately add the method etc. of tetracarboxylic dianhydride's composition and diamine component, can make By any means in these.During in addition, diamine component or tetracarboxylic dianhydride's composition comprise multiple compounds, can mix in advance React in the state of conjunction, it is also possible to react successively individually, the low-molecular weight reacted individually can also be made to occur Hybrid reaction and make HMW body.

Temperature when making diamine component and tetracarboxylic dianhydride's composition react can select arbitrary temperature, for example,- The scope of 20 DEG C～150 DEG C, preferably-5 DEG C～100 DEG C.In addition, reaction can be carried out under any concentration, for example, 1～50 Quality %, preferably 5～30 mass %.

The total mole number of the tetracarboxylic dianhydride's composition in above-mentioned polymerisation is relative to the ratio of the total mole number of diamine component Rate can select arbitrary value according to the molecular weight of the polyamic acid going for.In the same manner as common polycondensation reaction, this mole Become bigger than the molecular weight closer to 1.0 polyamic acids generating.If preferred scope must be exemplified, then be 0.8～ 1.2。

The synthetic method of the polyamic acid using in the present invention is not limited to said method, the conjunction with general polyamic acid One-tenth method similarly, uses the tetracarboxylic acid derivatives such as the tetrabasic carboxylic acid of corresponding construction or tetrabasic carboxylic acid two carboxylic acid halides to replace above-mentioned tetrabasic carboxylic acid Dianhydride, utilizes known method to react, it is also possible to obtain corresponding polyamic acid.

The method making polyimides as making above-mentioned polyamic acid carry out imidizate, can list: by polyamide The direct-fired hot-imide of solution of acid, the catalysis imidizate adding catalyst in the solution of polyamic acid.

In polyimides used in the present invention, the acid imide rate being changed into polyimides by polyamic acid not necessarily needs It is 100%.

Temperature when making polyamic acid carry out hot-imide in the solution is 100 DEG C～400 DEG C, be preferably 120 DEG C～ 250 DEG C, it is preferred that remove the water being generated by imidization reaction outside system, while it is sub-to carry out hot acyl Amination.

The catalysis imidizate of polyimide precursor can be by adding base catalysis in the solution of polyimide precursor Agent and acid anhydrides, with-20～250 DEG C, preferably carry out with 0～180 DEG C of stirring.The amount of base catalyst is the 0.5 of acid amides acidic group ～30 moles times, preferably 2～20 moles times, the amount of acid anhydrides is 1～50 mole times of acid amides acidic group, is preferably 3～30 moles Times.As base catalyst, can list pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., wherein, pyridine has right The alkalescence of appropriateness for advancing reaction, so preferably.As acid anhydrides, acetic anhydride, trihemellitic acid acid anhydride, pyromellitic acid can be listed Acid anhydride etc., wherein, when using acetic anhydride, reaction terminate after refined become easy, so preferably.Acyl based on catalysis imidizate Imines rate can be controlled by adjusting catalytic amount and reaction temperature, reaction time.

Reclaim generated polyimide precursor or polyamides is sub-from the reaction solution of polyimide precursor or polyimides During amine, can put into reaction solution makes it precipitate to poor solvent.As the poor solvent for precipitation, first can be listed Alcohol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc..Put into extremely bad Solvent and the polymer that is precipitated out, after being recovered by filtration, can carry out air drying or heat drying under normal or reduced pressure. In addition, the polymer making precipitation reclaim is dissolved in again organic solvent and carry out reprecipitation recovery operation repeat 2～10 times When, the impurity in polymer can be reduced.As poor solvent now, such as alcohols, ketone, hydrocarbon etc. can be listed, use During more than 3 kinds poor solvents among these, purification efficiency improves further, so preferably.

The aligning agent for liquid crystal of the present invention has above-mentioned [I] polymerizable compound and above-mentioned [II] polyimide precursor or polyamides Imines, in addition to this [I] and [II] composition, can also have the resinous principle for forming resin coating.All resins becomes The content dividing can be 1 mass %～20 mass % in 100 mass % aligning agent for liquid crystal, be preferably 3 mass %～15 matter Amount %, more preferably 3～10 mass %.

In aligning agent for liquid crystal used in the present invention, above-mentioned resinous principle can entirely have the polyimides of side chain A Precursor or polyimides or polyimide precursor or the polyimides with side chain A and side chain B, it is also possible to be the mixed of them Compound, and then, other polymer in addition can also be mixed with.Now, other polymer described in resinous principle Content is preferably 0.5 mass %～15 mass %, more preferably 1 mass %～10 mass %.

As other polymer described, can list and for example not there is the polyimide precursor of side chain B or polyimides, no There are polyimide precursor or the polyimides etc. of side chain A and side chain B simultaneously, but be not limited to them.

Polymer molecular weight with regard to above-mentioned resinous principle, it is contemplated that when coating strength therefrom and formation film When operability, film are all with property, with by GPC (gel permeation chromatography, Gel Permeation Chromatography) method The Weight-average molecular gauge measuring, is preferably set to 5000～1000000, and more preferably 10000～150000.

As long as the organic solvent using in the aligning agent for liquid crystal of the present invention dissolves the organic solvent of above-mentioned resinous principle, just It is not particularly limited.This organic solvent can be a kind of solvent, it is also possible to be mixed solvent of more than two kinds.If must list The concrete example of organic solvent, then can list the organic solvent exemplifying in foregoing polyamides acid synthesis.Wherein, become from resin Point dissolubility from the viewpoint of, preferably METHYLPYRROLIDONE, gamma-butyrolacton, N-ethyl-2-pyrrolidone, 1,3- Dimethyl-2-imidazolinone, 3-methoxyl group-N, N-dimethylpropionamide.

In addition, such solvent described below can improve the uniformity of film, flatness, it is therefore preferable that mixing is to resin The high solvent of the dissolubility of composition uses.

For example can list isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, first Base cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl card Must alcohol acetic ester, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propane diols, propane diols list Acetic acid esters, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propane diols-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl two Alcohol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, DPG list first Ether, propylene glycol methyl ether acetate, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, two Propylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxyl group fourth Alcohol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, DIBK, methylcyclohexene, Propyl ether, hexyl ether, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid second Ester, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-second Epoxide propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-ethyoxyl-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2- The single ether of propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propane diols-1-monomethyl ether-2-acetic acid esters, propane diols-1-- 2-acetic acid esters, DPG, 2-(2-ethoxy-c epoxide) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, lactic acid are just Butyl ester, isoamyl lactate, 2-ethyl-1-hexanol etc..These solvents can mix multiple.When using these solvents, preferably liquid 5～80 mass % of the solvent entirety comprising in brilliant alignment agent, more preferably 20～60 mass %.

Aligning agent for liquid crystal can contain composition other than the above.As its example, coating of liquid crystalline orientation of sening as an envoy to can be enumerated The compound that film thickness uniformity during agent, surface smoothness improve；Make the chemical combination of liquid crystal orientation film and the adaptation raising of substrate Thing etc..

As the compound making film thickness uniformity, surface smoothness improve, fluorine system surfactant, organosilicon can be listed It is surfactant, anion system surfactant etc..More specifically, for example can list Eftop EF301, EF303, EF352 (Tohkem products Corporation system), Megafac F171, F173, R-30 (big Japanese ink strain formula meeting Society's system), Fluorad FC430, FC431 (Sumitomo 3M Limited system), AsahiGuard AG710, Surflon S- 382nd, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's system) etc..Use these surface-actives During agent, its use ratio relative to resinous principle 100 mass parts containing in aligning agent for liquid crystal, preferably 0.01～2 mass parts, More preferably 0.01～1 mass parts.

As the concrete example of the compound making the adaptation with substrate for the liquid crystal orientation film improve, silicon containing functionality can be listed The compound of alkane, the compound etc. containing epoxy radicals.For example can list 3-TSL 8330,3-aminopropyl three Ethoxysilane, 2-TSL 8330,2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-ammonia Base propyl trimethoxy silicane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-urea propyl trimethoxy Silane, 3-urea propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3- Aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide triethylene triamine, N-trimethoxy-silylpropyl Triethylene triamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three Azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-phenodiazine Miscellaneous nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-benzene Double (oxygen the ethene)-3-aminopropan of base-3-TSL 8330, N-phenyl-APTES, N- Base trimethoxy silane, N-double (oxygen ethene)-APTES, ethylene glycol diglycidylether, poly-second two Alcohol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol Diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-isophthalic diformazan Amine, 1,3-double (N, N-diglycidyl amino methyl) hexamethylene, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminourea Diphenyl methane, 3-(N-pi-allyl-N-glycidyl) TSL 8330,3-(N, N-diglycidyl) TSL 8330 etc..In addition, for the resistance to brushing improving the resin employing the present invention further, it is also possible to Add 2,2 '-bis-(4-hydroxyl-3,5-bishydroxymethyl phenyl) phenolic compounds such as propane, four (methoxy) bis-phenol.Use During these compounds, relative to resinous principle 100 mass parts containing in aligning agent for liquid crystal, preferably 0.1～30 mass parts, more It is preferably 1～20 mass parts.

In aligning agent for liquid crystal used in the present invention, in addition to that mentioned above, as long as in the scope not damaging effect of the present invention In, then can add for change liquid crystal orientation film dielectric constant, the dielectric of the electrical characteristics such as electric conductivity, conductive materials.

It after the aligning agent for liquid crystal of the present invention is coated substrate, is dried as required, burns till, thus obtained solidification Film also can be directly used as liquid crystal orientation film.Alternatively, it is also possible to carry out brushing to this cured film or irradiate polarised light or specific Light of wavelength etc. or carry out the process of ion beam etc. or make SC-PVA alignment films the liquid after to filling liquid crystal Brilliant expression element applies to irradiate UV in the state of voltage.

Now, as substrate used thereof, as long as the high substrate of the transparency is just not particularly limited, it is possible to use glass plate, Merlon, poly-(methyl) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfones, polyethers, polyether-ketone, trimethylpentene, poly- Alkene, polyethylene terephthalate, (methyl) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate fiber Element etc..In addition, from the viewpoint of Simplified flowsheet, be preferably used be formed for drive liquid crystal ITO (tin indium oxide, Indium Tin Oxide) substrate of electrode etc..In addition, for the liquid crystal of reflection-type represents element, if being only unilateral base Plate, then also can use the opaque materials such as silicon wafer, and electrode now also can use aluminium etc. can reflect the material of light.

The coating process of aligning agent for liquid crystal is not particularly limited, and can list serigraphy, hectographic printing, flexible printing etc. Print process, ink-jet method, spray-on process, rolling method, dipping, roll coater, slit coater, spin coater etc..Go out in terms of productive Send out, be widely used in industry hectographic printing method, it is possible to be applicable to the present invention.

The film utilizing said method coating of liquid crystalline alignment agent and being formed can burn till and make cured film.Coating of liquid crystalline takes Drying process after agent is not necessarily necessary, but each substrate when after being coated with, time to burning till is not fixed or It when not burning till immediately after person's coating, is preferably dried operation.Will not be because of base to film shape by solvent removal as long as this is dried The conveyances of plate etc. and the degree that deforms, be dried means for it and be not particularly limited.For example can list temperature 40 DEG C It is dried the method for 0.5 minute～30 minutes, preferably 1 minute～5 minutes on the hot plate of～150 DEG C, preferably 60 DEG C～100 DEG C.

The firing temperature of the film being formed by coating of liquid crystalline alignment agent is not limited, for example can be at 100～350 DEG C Arbitrary temp under carry out, preferably 120 DEG C～300 DEG C, more preferably 150 DEG C～250 DEG C.Firing time can be 5 Minute～random time of 240 minutes in burn till.Preferably 10 minutes～90 minutes, more preferably 20 minutes～90 points Clock.Heating can utilize generally well-known method, such as hot plate, recirculation furnace, infrared heating heating furnace etc. to carry out.

In addition, the thickness of liquid crystal orientation film obtained from burning till is not particularly limited, preferably 5～300nm, more preferably 10～120nm.

After the liquid crystal of the present invention represents that element can form liquid crystal orientation film by said method on substrate, utilize known Method makes liquid crystal cells and obtains.Represent the concrete example of element as liquid crystal, for possessing the vertical orientated of following liquid crystal cells The liquid crystal of mode represents element, and described liquid crystal cells possesses: two plate bases of relative configuration, setting liquid crystal between the substrates The above-mentioned liquid crystal orientation film that layer and the aligning agent for liquid crystal utilizing the present invention arranging between substrate and liquid crystal layer are formed.Tool For body, the liquid crystal of the vertical orientation mode for possessing following liquid crystal cells represents element, and described liquid crystal cells is following making : by being coated on the aligning agent for liquid crystal of the present invention on two plate bases and burn till, thus form liquid crystal orientation film, with this liquid crystal The relative mode of alignment films configures two plate bases, clamps the liquid crystal layer being made up of liquid crystal, i.e. Fluid Contacting between this two plate base Brilliant alignment films liquid crystal layer is set, applies voltage irradiation ultraviolet radiation on one side to liquid crystal orientation film and liquid crystal layer, thus make. Like this, use the liquid crystal orientation film being formed by the aligning agent for liquid crystal of the present invention, liquid crystal orientation film and liquid crystal layer are applied Voltage, irradiation ultraviolet radiation, while making polymerizable compound be polymerized, make the photoreactivity side chain that polymer has each other The photoreactivity side chain that reaction, polymer have reacts with polymerizable compound, so that the orientation of liquid crystal is more effectively fixed Change, become the substantially excellent liquid crystal of response speed and represent element.

Liquid crystal as the present invention represents the substrate using in element, as long as the high substrate of the transparency does not just limit especially Fixed, it is common that on substrate, to be formed with the substrate of transparency electrode for driving liquid crystal.As concrete example, can list with above-mentioned The identical substrate of substrate described in liquid crystal orientation film.The existing substrate being provided with electrode pattern, projection pattern can be used, Liquid crystal in the present invention represents in element, as the aligning agent for liquid crystal forming liquid crystal orientation film, employs the liquid of the invention described above Brilliant alignment agent, therefore, even forming the line/gap electrode pattern of such as 1～10 μm, and not at opposite substrate at single sided substrate Form slit pattern, the structure of projection pattern also can work, and represents element by the liquid crystal of this structure, when can simplify manufacture Technique, be obtained in that high-transmission rate.

In addition, for the high function element of the element etc of TFT type, it is possible to use at the electrode for driving liquid crystal And it is formed the expression element of the element of transistor etc between substrate.

In the case that transmission-type liquid crystal represents element, generally use substrate as described above, represent at reflective liquid crystal In the case of element, if only single sided substrate, then also can use the opaque substrates such as silicon wafer.Now, it is formed at substrate Electrode also can use can the material of the aluminium reflecting light etc.

Liquid crystal orientation film can carry out burning till being formed after being coated with the aligning agent for liquid crystal of the present invention on the substrate, details As mentioned above.

The liquid crystal of the present invention represents that the liquid crystal material of the composition liquid crystal layer of element is not particularly limited, it is possible to use existing Liquid crystal material, MLC-6608, MLC-6609 etc. of such as MERCK CORPORATION manufacture of using in vertical orientation mode bear Type liquid crystal.

As the method making this liquid crystal layer be clamped between two plate bases, known method can be listed.For example can enumerate Go out: prepare to be formed with 1 pair of substrate of liquid crystal orientation film, the liquid crystal orientation film of a substrate spreads pearl thing at equal intervals, with Being formed with the surface of liquid crystal orientation film side becomes the mode of inner side and pastes another substrate, and liquid crystal the side sealing are injected in decompression Method.In addition, by preparing to be formed with 1 pair of substrate of liquid crystal orientation film, the liquid crystal orientation film of a substrate spreads pearl etc. After sept, drip liquid crystal, in the way of the surface being formed with liquid crystal orientation film side becomes inner side, paste another base thereafter Plate, and the method sealing, it is also possible to make liquid crystal cells.The thickness of sept now be preferably 1～30 μm, more preferably It is 2～10 μm.

By while the work that applies voltage irradiation ultraviolet radiation on one side to liquid crystal orientation film and liquid crystal layer and make liquid crystal cells Sequence can list following method: for example by be arranged between the electrode on substrate applying voltage and to liquid crystal orientation film and liquid crystal Layer applies electric field, the method for irradiation ultraviolet radiation under conditions of keeping this electric field.Herein, as putting on interelectrode voltage, For example, 5～30Vp-p, preferably 5～20Vp-p.Ultraviolet irradiation amount for example, 1～60J/cm², be preferably 40J/cm²With Under, more preferably 20J/cm²Below.When ultraviolet irradiation amount is few, can suppress to represent because constituting liquid crystal element liquid crystal, The breakage of parts and the reliability that produces reduces, and make manufacture efficiency improve by reducing ultraviolet irradiation time, so fitting Close.

Like this, when voltage irradiation ultraviolet radiation on one side being applied to liquid crystal orientation film and liquid crystal layer, polymerizable compound Reacting and forming polymer, the incline direction remembeing liquid crystal molecule by this polymer, therefore, it is possible to accelerate gained liquid The brilliant response speed representing element.In addition, during while apply voltage irradiation ultraviolet radiation on one side to liquid crystal orientation film and liquid crystal layer, choosing Carry out polyimides obtained from imidizate from the polyimide precursor with reactive side chain with by this polyimide precursor In the photoreactivity side chain that photoreactivity side chain reacts with each other, polymer is had that had of at least one polymer with poly- Conjunction property compound reacts, therefore, it is possible to accelerate the response speed that gained liquid crystal represents element.

In addition, above-mentioned aligning agent for liquid crystal serves not only as making PSA type liquid crystal display, SC-PVA type liquid crystal display Deng the liquid crystal of vertical orientation mode represent that the aligning agent for liquid crystal of element is useful, even by brushing process, light orientation The purposes of the liquid crystal orientation film processing and making also can compatibly use.

Hereinafter, further illustrate the present invention by embodiment, but the present invention is not limited to these embodiments.

Embodiment

The abbreviation using when preparing following aligning agent for liquid crystal is as follows.

(acid dianhydride)

BODA: bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride.

CBDA:1,2,3,4-cyclobutane tetracarboxylic dianhydride.

PMDA: PMDA.

TCA:2,3,5-tricarboxylic cyclopentyl acetic acid-1,4,2,3-dianhydride.

The method that diamines shown in following formula DA-1 is recorded by Japanese Patent Publication No. 4085206 synthesizes.

The method that diamines shown in following formula DA-2 is recorded by Japanese Patent Publication No. 4466373 synthesizes.

The method that diamines shown in following formula DA-3 is recorded by Japanese Patent Publication No. 5273035 synthesizes.

Diamines shown in following formula DA-4 buys the product that Tokyo HuaCheng Industry Co., Ltd manufactures.

Diamines shown in following formula DA-5 is synthesized by the method that WO2009/093704 records.

Prepared by the method that the diamines shown in following formula DA-6 is recorded by Japanese Patent Application 2013-132874.

Diamines shown in following formula DA-7 buys the product that Wako Pure Chemical Industries, Ltd. manufactures.

Prepared by the method that the diamines shown in following formula DA-8 is recorded by Japanese Patent Application 2013-182351.

Diamines shown in following formula DA-9 is by the method system described in aftermentioned (synthesis of Material synthesis example: DA-9) Standby.

NMP:N-N-methyl-2-2-pyrrolidone N.

BCS: butyl cellosolve.

3AMP:3-pyridyl-methanamine.

Polymerizable compound shown in following formula RM1～RM10 and RM11.

In addition, the molecule measuring fixed condition of polyimides is as follows.

Device: Senshu Scientific co., ltd. normal temperature gel permeation chromatography (GPC) device (SSC-7200),

Post: Shodex company manufacture post (KD-803, KD-805),

Column temperature: 50 DEG C,

Eluent: N, N '-dimethyl formamide is (as additive, lithium bromide monohydrate (LiBr H₂O) it is 30mmol/L, phosphoric acid anhydrous crystalline (orthophosphoric acid) be 30mmol/L, oxolane (THF) be 10ml/L),

Flow velocity: 1.0ml/ minute,

Standard curve making standard sample: (molecular weight is about TOSOH Co., Ltd TSK standard PEO 9000000th, the 150000th, the 100000th, 30000) and the polyethylene glycol (molecular weight that manufactures of Polymer Laboratories Ltd. It is about the 12000th, the 4000th, 1000).

In addition, the acid imide rate of polyimides operates as follows and measures.Put into polyimide powder 20mg to NMR sample QC (wasteland's science Co., Ltd. NMR sample cell specification, φ 5), adds deuterated dimethyl sulfoxide (DMSO-d₆, 0.05% TMS melange) 1.0ml, make it be completely dissolved with ultrasonic wave.Utilize the NMR analyzer (JNW-that JEOL DATUM company manufactures ECA500) the proton NMR of 500MHz is measured to this solution.The knot that acid imide rate does not changes before and after being derived from imidizate The proton of structure determines as reference proton, uses peak integrated value and the neighbouring source occurring of 9.5ppm～10.0ppm of this proton Following formula is utilized to obtain from the proton peak integrated value of the NH base of amic acid.It should be noted that in following formula, x is for being derived from acyl When on the basis of the proton peak integrated value of the NH base of amino acid, y, the peak integrated value of proton, α are polyamic acid (acid imide rate is 0%) Reference proton relative to the NH matrix son number ratio of 1 of amic acid.

Acid imide rate (%)=(1-α x/y) × 100

Product described in following synthesis example passes through¹H-NMR analyzes and carries out identifying (analysis condition is as follows).

Device: Varian NMR System 400NB (400MHz)

Measure solvent: CDCl₃、DMSO-d₆

Primary standard substance: tetramethylsilane (TMS) (δ 0.0ppm for¹H)

(synthesis of Material synthesis example: DA-9)

In 1000mL four-neck flask, in 600g THF, put into cholesterol 120g (310mmol, 1.0eq) and triethylamine 33.3g (329mmol, 1.1eq), expends 1 hour and adds 3,5-dinitrobenzoyl chloride 69.2g (300mmol).After interpolation, whole After night is stirred at room temperature, water is utilized to carry out reprecipitation.Gained solid is recrystallized by IPA and ethyl acetate respectively, Crude product 179g (thick yield: 100%) to DA-9-1.

¹H-NMR(CDCl₃, δ ppm): 9.22 (s, 1H), 9.16 (s, 2H), 5.46-5.44 (m, 1H), 5.00-4.95 (m, 1H),2.56-2.48(m,2H),2.06-1.95(m,4H),1.87-1.81(m,2H),1.63-0.86(m,32H),0.70(s, 3H).

In 2000mL four-neck flask, in 750gTHF and 750g pure water, put into DA-9-1 146g (251mmol), chlorination Tin 284g (1497mmol, 6.0eq), stirs at 70 DEG C whole night.It after reaction terminates, is neutralized, is removed institute by filtration The tin separating out.Thereafter, separatory utilize IPA to recrystallize, obtains DA-9 76.3g (yield: 58%).

¹H-NMR(CDCl₃, δ ppm): 6.78 (s, 2H), 6.18 (s, 1H), 5.42-5.40 (m, 1H), 4.84-4.77 (m, 1H),3.67(s,4H),2.43(d,2H),1.63-0.86(m,38H),0.69(s,3H).

In the 1L four-neck flask possessing magnetic stirring apparatus, in 350g THF and 117g water, put into 4-bromo-2-fluorophenol 58.3g (305mmol) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate-2-base) phenol 67.2g (1.0eq), carbonic acid Potassium 84.8g (2.0eq), three (o-tolyl) phosphine 7.42g (8mol%), add double (triphenylphosphine) palladium bichloride after nitrogen displacement (II) 10.9g (5mol%), reacts 15 hours with 65 DEG C.

After reaction terminates, distilled removal THF by reduced pressure concentration, after ethyl acetate 466g dilution, add 3.0M HCl/water solution 268g, is removed the insoluble matters such as Pd by filtration, uses ethyl acetate 233g to carry out flask, filtrate further Cleaning.Then, separate aqueous phase and reclaim organic phase, the organic phase reclaiming is cleaned 3 times by pure water 350g, carries out with magnesium sulfate After processed, add activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 2.92g, It is stirred at room temperature about 30 minutes, carry out filtration drying, thus obtain crude product.By crude product toluene 292g at room temperature bar After carrying out repulped twice cleaning under part, carry out filtration drying, thus obtain RM1-A 42.0g (yield: the 67%th, proterties: light powder The crystal of look).

¹H-NMR(400MHz)in DMSO-d₆: 6.80ppm (dd, J=2.0Hz, J=6.8Hz, 2H), 6.97ppm (t, J =8.8Hz, 1H), 7.21ppm (dd, J=2.0Hz, J=8.4Hz, 1H), 7.35ppm (dd, J=2,4Hz, J=13.2Hz, 1H), 7.42ppm (dd, J=2.0Hz, J=6.4Hz, 2H), 9.49ppm (s, 1H), 9.82ppm (s, 1H).

In the 200ml four-neck flask possessing magnetic stirring apparatus, 80ml acetone puts into compound obtained above (RM1-A) 6.00g (24.5mmol) and 2-(4-brombutyl)-1,3-dioxolanes 12.0g (2.2eq), potassium carbonate 13.8g (4.0eq), react 24 hours with 60 DEG C.Thereafter, by by reaction solution input to pure water makes crystal separate out, filtering It is dried, thus obtain RM1-B 10.4g (yield: 92%).

¹H-NMR(400MHz)in CDCl₃: 1.60-1.67ppm (m, 4H), 1.71-1.78ppm (m, 4H), 1.82- 1.93ppm (m, 4H), 3.82-4.10ppm (m, 12H), 4.89ppm (t, J=4.6Hz, 2H), 6.92-7.00ppm (m, 3H), 7.20-7.30ppm (m, 2H), 7.43ppm (d, J=8.8Hz, 2H).

In the 100ml four-neck flask possessing magnetic stirring apparatus, 40mlTHF puts into compound obtained above (RM1-B) 2.90g (6.30mmol) and 2-(bromomethyl) acrylic acid 2.5g (2.4eq), stannic chloride (anhydride) 2.8g (2.4eq), add 10%HCl aqueous solution 12ml, react 20 hours with 70 DEG C.Thereafter, by putting into reaction solution to pure water And make crystal separate out, carry out filtration drying and obtain crude product.By recrystallizing gained crude product in THF/EtOH, Thus obtain RM1 2.2g (yield: 69%).

¹H-NMR(400MHz)in CDCl₃: 1.55-1.93ppm (m, 12H), 2.61ppm (dd, J=7.6Hz, J= 18.4Hz, 2H), 3.09ppm (dd, J=6.8Hz, J=16.6Hz, 2H), 4.00ppm (t, J=6.2Hz, 2H), 4.08ppm (t, J=6.4Hz, 2H), 4.35-4.60ppm (m, 2H), 5.64ppm (s, 2H), 6.24ppm (s, 2H), 6.93-7.01ppm (m, 3H), 7.22-7.289ppm (m, 2H), 7.45ppm (d, J=8.8Hz, 2H).

In the 1L four-neck flask possessing magnetic stirring apparatus, in 281g THF, put into 2-hydroxyethyl methacrylate 70.2g (539mmol), triethylamine 76.4g (1.4eq), drip the methane sulfonyl chloride with THF35.1g dilution under ice-cold stirring It after 74.6g (1.2eq), is stirred at room temperature 2 hours.Thereafter, filter the salt separating out from reactant liquor, in filtrate, add two fourths Base hydroxy-methylbenzene 0.35g, carries out concentrate drying.Then, in concentrate residue, add ethyl acetate 281g, add pure water 210g When, produce insoluble matter, therefore add activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 3.5g, is stirred at room temperature 30 minutes.Then, after being filtered and confirm that insoluble matter is removed, aqueous phase is removed.And then, will have Machine pure water 210g cleans 2 times, after carrying out processed with magnesium sulfate, carries out concentrate drying, thus obtains RM2-A 99.0g (yield: the 86%th, proterties: yellow liquid).

¹H-NMR(400MHz)in CDCl₃: 1.93-1.94ppm (m, 3H), 3.03ppm (s, 3H), 4.39-4.41ppm (m,2H),4.46-4.44ppm(m,2H),5.61-5.62ppm(m,1H),6.15(m,1H).

In the 300ml four-neck flask possessing magnetic stirring apparatus, 72.8g THF and 31.2g pure water put into the bromo-2-of 4- Fluorophenol 10.4g (54.4mmol) and 6-hydroxyl-2-naphthalene boronic acids 9.68g (1.0eq), potassium carbonate 15.1g (2.0eq), three (adjacent first Phenyl) phosphine 1.32g (8mol%), adds double (triphenylphosphine) palladium bichloride (II) 1.91g (5mol%), with 65 after nitrogen displacement DEG C reaction 2 hours.Thereafter, removed THF by reduced pressure concentration, after ethyl acetate 104g dilution, add 3.0M HCl/water molten Liquid 47.8g simultaneously stirs.Then, removed Pd by filtration, and then after using the ethyl acetate cleaned screening of 52.0g etc., separate Aqueous phase.The organic phase reclaiming is cleaned 3 times by pure water 72.8g, after carrying out processed with magnesium sulfate, interpolation activated carbon (trade mark: Special egression dry product Japan EnviroChemicals, Ltd. system) 0.52g, it is stirred at room temperature about 1 hour, carried out It is filtered dry dry.After crude product toluene 72.8g is carried out repulped cleaning, by Silica hydrogel column chromatography (ethyl acetate/toluene/own Alkane (=1/1/2vol)) refine, thus obtain RM2-B 6.47g (yield: the 49%th, proterties: white solid).

¹H-NMR(400MHz)in DMSO-d₆: 7.03-7.13ppm (m, 3H), 7.42-7.40ppm (m, 1H), 7.57ppm (dd, J=13Hz, J=2.2Hz, 1H), 7.67ppm (dd, J=8.6Hz, J=1.8Hz, 1H), 7.72ppm (d, J=8.4Hz, 1H), 7.80ppm (d, J=8.4Hz, 1H), 8.01ppm (s, 1H), 9.78ppm (s, 1H), 9.96ppm (s, 1H).

In the 200mL four-neck flask possessing magnetic stirring apparatus, DMF48.6g puts into compound obtained above (RM2-B) 6.07g (23.9mmol) and polymerism side chain (RM2-A) 11.1g (2.2eq), potassium carbonate 9.93g (3.0eq), at nitrogen React 22 hours with 65 DEG C under gas atmosphere.

Thereafter, with after ethyl acetate 48.6g diluting reaction solution, after removing inorganic salts by filtration, filtrate is used Ethyl acetate 42.5g is carried out.The organic phase reclaiming is cleaned 3 times by pure water 48.6g, organic phase magnesium sulfate is taken off After water is processed, carry out concentrate drying.After drying, in the crude product reclaiming, add BHT 12.1mg, add Add THF 5.77g and heat with 45 DEG C so that it is being completely dissolved, add methyl alcohol 35.8g and recrystallize with 5.0 DEG C.But It is to confirm impurity, therefore, in the solid reclaiming, add THF 4.89g and heat with 45 DEG C so that it is being completely dissolved, add Add methyl alcohol 24.9g and recrystallize with room temperature, thus obtaining RM2 6.37g (yield: the 56%th, proterties: white crystal).

¹H-NMR(400MHz)in DMSO-d₆: 1.89ppm (s, 6H), 4.38-4.42ppm (m, 4H), 4.46-2.47ppm (m, 2H), 4.49-4.51ppm (m, 2H), 5.70-5.71ppm (m, 2H), 6.05ppm (d, J=6.8Hz, 2H), 7.22ppm (dd, J=9.0Hz, J=2.8Hz, 1H), 7.33ppm (t, J=9.0Hz, 1H), 7.40ppm (d, J=2.4Hz, 1H), 7.59ppm (d, J=9.6Hz, 1H), 7.70ppm (dd, J=12.8Hz, J=2.0Hz, 1H), 7.80ppm (dd, J=8.6Hz, J=1.8Hz, 1H), 7.88ppm (t, J=9.2Hz, 2H), 8.15ppm (s, 1H).

In the 2L four-neck flask possessing mechanical agitator, 179g THF and 76.6g pure water put into the bromo-2-of Isosorbide-5-Nitrae-two Fluorobenzene 25.5g (101mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate-2-base) phenol 45.5g (2.0eq), Potassium carbonate 41.7g (3.0eq), double (triphenylphosphine) palladium bichloride (II) 2.12g, stir 24 hours with 65 DEG C in a nitrogen atmosphere. Thereafter, distilled removal THF by reduced pressure concentration, reaction solution is diluted by ethyl acetate 255g, add 3.0M HCl/water molten Liquid 99.5g, is removed the insoluble matters such as Pd by filtration.Remove after aqueous phase from filtrate, by clear for gained organic phase pure water 179g Wash 3 times.The organic phase magnesium sulfate of recovery is carried out processed, adds activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 1.30g, after stirring about 30 minutes at ambient temperature, carry out filtration drying and obtain Crude product.The crude product making recovery is suspended in toluene 153g, carries out the repulped cleaning of 60 DEG C, 1 hour 2 times, filters It is dried, thus obtain RM3-A 22.4g (yield: 79%, proterties: pale pink crystal).

¹H-NMR (400MHz) in DMSO-d6:6.85-6.88ppm (m, 4H), 7.41ppm (dd, J=1.2Hz J= 8.4Hz, 2H), 7.46-7.49ppm (m, 3H), 7.57ppm (d, J=8.8Hz, 2H), 9.65ppm (s, 2H).

In the 500mL four-neck flask possessing mechanical agitator, 113g DMF puts into polymerism side chain (RM2-A) 23.0g (2.2eq) and compound obtained above (RM3-A) 14.1g (50.2mmol), potassium carbonate 20.9g (3.0eq), at nitrogen Stir 18 hours with 65 DEG C under gas atmosphere.Remain raw material after 18 hours, therefore, add polymerism side chain (RM2-A) (0.2eq/ 2) go forward side by side single step reaction 4 hours.Thereafter, by reaction solution with after ethyl acetate 113g dilution, inorganic salts are removed by filtration After, filtrate ethyl acetate 70.5g is carried out.Clean the organic phase reclaiming with pure water 141g, result produces trace White crystal, therefore, add ethyl acetate 70.5g, further with pure water 141g clean 2 times, organic phase magnesium sulfate is entered Row processed, carries out filtration drying.Add activated carbon (trade mark: special egression dry product Japan in the crude product reclaiming EnviroChemicals, Ltd. system) 0.71g, after stirring about 30 minutes at ambient temperature, carry out filtration drying, add vinegar Acetoacetic ester 222g simultaneously heats with 50 DEG C, so that it is completely dissolved, adds hexane 98.2g, recrystallizes with 2 DEG C, from And obtain RM3 15.0g (yield: 59%, proterties: white crystal).

¹H-NMR(400MHz)in DMSO-d6:1.89ppm(s,6H),4.30-4.33ppm(m,4H),4.45- 4.46ppm(m,4H),5.71ppm(s,2H),6.05ppm(s,2H),7.07-7.10ppm(m,4H),7.52-7.56ppm(m, 5H), 7.70ppm (d, J=8.4Hz, 2H).

In the 300mL four-neck flask possessing magnetic stirring apparatus, 73.4g DMF puts into fluorine-containing diphenol compound (RM1-A) 9.18g (45.0mmol) and potassium carbonate 18.6g (3.0eq), polymerism side chain (RM2-A) 20.7g (2.2eq), at nitrogen React 15 hours with 62 DEG C under gas atmosphere.Thereafter, reaction solution ethyl acetate 138g is diluted, is removed by filtration Inorganic salts.Add ethyl acetate 45.9g further in the filtrate reclaimed, clean 3 times with pure water 91.8g, carry out with sodium sulphate Processed.Then, activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) is added 0.46g, after being stirred at room temperature about 30 minutes, filters to it, filtrate is carried out concentrate drying.Add in concentrate BHT 9.2mg, adds IPA 184g and is heated to 57 DEG C so that it is being completely dissolved, enter at ambient temperature Row recrystallization, thus obtain RM4 13.4g (yield: the 70%th, proterties: light yellow crystal).

¹H-NMR(400MHz)in DMSO-d6:1.87-1.88ppm(m,6H),4.27-4.29ppm(m,2H),4.34- 4.37ppm (m, 2H), 4.43-4.46ppm (m, 4H), 5.69-5.70ppm (m, 2H), 6.03ppm (d, J=4.8Hz, 2H), 7.03ppm (d, J=8.8Hz, 2H), 7.25ppm (t, J=8.8Hz, 1H), 7.39ppm (dd, J=1.6Hz, J=8.4Hz, 1H), 7.50ppm (dd, J=2.0Hz, J=13Hz, 1H), 7.58ppm (d, J=8.8Hz, 2H).

Above-mentioned RM5 synthesizes according to No. WO2012/002513 method recorded.

Above-mentioned RM6 synthesizes according to No. WO2012/133820 method (referring in particular to [0163rd] section) recorded.

In the 200mL four-neck flask possessing magnetic stirring apparatus, 18g NMP puts into fluorine-containing diphenol compound (RM1-A) 9.00g (44.1mmol), acetyl bromide dimethylacetal 22.4g (3.0eq), potassium carbonate 24.4g (4.0eq), KI 2.2g (0.30eq), stirs 18 hours with 120 DEG C.After 18 hours, acetyl bromide dimethylacetal 7.45g (1.0eq), iodate are added Potassium 1.4g (0.2eq), stirs 8 hours further.After reaction terminates, reaction solution is diluted by THF 99.0g, filtering inorganic salt After, reduced pressure concentration is carried out to filtrate.Then, this residue is diluted by ethyl acetate 198g, after cleaning 2 times with pure water 99.0g, use Magnesium sulfate carries out processed.Thereafter, add activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 0.45g, it is stirred at room temperature 1 hour, it is filtered, filtrate is carried out reduced pressure concentration.Then, thick to gained Product adds THF 19.8g, after making it dissolve with 50 DEG C, adds IPA 60.3g, be stirred under ice-cold.To thus analyse The crystal going out carries out filtration drying, thus obtains RM7-A 11.5g (yield: the 62%th, proterties: filbert crystal).

¹H-NMR(400MHz)in DMSO-d₆: 3.36ppm (m, 12H), 4.01ppm (d, J=5.2Hz, 2H), 4.08ppm (d, J=5.2Hz, 2H), 4.74-4.69ppm (m, 2H), 7.03ppm (d, J=11.6Hz 2H), 7.25ppm (t, J=8.8Hz 1H), 7.40-7.37ppm (m, 1H), 7.51ppm (dd, J=13Hz, J=2.2Hz 1H), 7.58ppm (d, J=8.4Hz 2H).

In the 500mL four-neck flask possessing magnetic stirring apparatus, 103g THF puts into compound obtained above (RM7-A) 10.4g (27.2mmol), 2-(bromomethyl) ethyl acrylate 11.6g (2.2eq), stannic chloride 12.4g (2.4eq), 10wt%HCl aqueous solution 36.2g, stirs 39 hours with 70 DEG C.After reaction terminates, add BHT 30mg, THF is removed in decompression distillation, is diluted with ethyl acetate 104g.After removal thus isolated aqueous phase, with 40 DEG C by organic phase Clean 3 times with pure water 62.4g.Then, after organic phase magnesium sulfate being carried out processed, activated carbon (trade mark: special in vain is added Aigret dry product Japan EnviroChemicals, Ltd. system) 0.52g, it is stirred at room temperature 1 hour, filtered, to filtrate Carry out reduced pressure concentration removal.Then, in gained crude product, add THF 52g, after making it dissolve with 60 DEG C, add EtOH 156g, is stirred under ice-cold.Thus, the crystal of precipitation is carried out filtration drying, thus obtain RM7 3.42g (yield: 30%th, proterties: white crystal).

¹H-NMR(400MHz)in DMSO-d₆: 2.88-2.50ppm (m, 2H), 3.17-2.11ppm (m, 2H), 4.14ppm (dd, J=5.6Hz, 11.2Hz, 1H), 4.28-4.20ppm (m, 2H), 4.33ppm (dd, J=2.8Hz, 11.0Hz, 1H), 5.00-4.95ppm (m, 2H), 6.99ppm (d, J=6.8Hz, 2H), 7.22ppm (t, J=8.8Hz, 1H), 7.41ppm (d, J =8.4Hz, 1H), 7.52ppm (dd, J=2Hz, 12.8Hz, 1H), 7.61ppm (d, J=2.0Hz, 2H).

In the 200mL four-neck flask possessing magnetic stirring apparatus, in 15.3g NMP, put into fluorine-containing diphenol compound (RM1-A) 10.0g (53.7mmol), potassium carbonate 20.4g (3.0eq), KI 1.61g (0.20eq), in a nitrogen atmosphere with 80 DEG C of 4-chlorobutyraldehyde dimethylacetal 16.6g (2.2eq) expending dropping NMP 5.30g dilution in 3 hours.After dripping 19 hours, Add 4-chlorobutyraldehyde dimethylacetal 2.25g (0.3eq) and KI 1.61g (0.2eq), react 25 hours further.Reaction knot Shu Hou, with ethyl acetate 80.0g diluting reaction solution, is removed potassium carbonate by filtration.And then, add ethyl acetate 20.0g, After cleaning 3 times with pure water 60.0g, carry out processed with magnesium sulfate.Thereafter, solvent is removed by reduced pressure concentration, thus To crude product.Gained crude product is added THF 10g and MeOH 70g, with 50 DEG C of heating, carries out ice-cold and make crystal separate out, enter Row filtration drying and obtain RM8-A11.7g (yield: the 55%th, proterties: white solid).In addition, filtrate is carried out reduced pressure concentration and Remove solvent, crude product is added THF5g and IPA 70g, with 40 DEG C of heating, carries out ice-cold and make crystal separate out, thus obtain RM8-A 3.0g (yield the 14%th, proterties: faint yellow solid).

¹H-NMR(400MHz)in DMSO-d₆:1.77-1.67ppm(m,8H),3.23ppm(s,12H),4.01ppm(t,J =6Hz, 2H), 4.08ppm (t, J=6Hz, 2H), 4.44-4.41ppm (m, 2H), 6.97ppm (d, J=6.8Hz, 2H), 7.19ppm (t, J=8.8Hz, 1H), 7.38ppm (d, J=7.6Hz, 1H), 7.48ppm (dd, J=13.2Hz, 2.4Hz, 1H), 7.56ppm (d, J=8.8Hz, 2H).

In the 300mL four-neck flask possessing magnetic stirring apparatus, in 133g THF, put into compound obtained above (RM8-A) 13.2g (30.3mmol), 2-(bromomethyl) ethyl acrylate 12.9g (2.2eq), stannic chloride 13.8g (2.4eq), 10wt%HCl aqueous solution 46.3g, reacts 5 hours with 50 DEG C.After 5 hours, add 20wt%HCl aqueous solution 13.2g so that it is anti- Answer 19 hours.After reaction terminates, THF is removed in decompression distillation, after ethyl acetate 106g dilution, carries out 3 water with pure water 52.8g Clean.Then, and then add ethyl acetate 26.4g and pure water 79.2g, add sodium acid carbonate and simultaneously neutralize.After neutralization, by filtering And remove desalination, in filtrate, add activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 0.70g, is stirred at room temperature and filters.After gained solution is cleaned 2 times with pure water 66g, removed solvent by reduced pressure concentration, Add THF 79.2g and IPA 158g, with 50 DEG C of heating, carry out ice-cold and make crystal separate out, carry out filtering and reclaiming crystal.Will Gained crystal adds THF 46.2g and MeOH92.4g, with 50 DEG C of heating, carries out ice-cold and makes crystal separate out, carry out filtration drying And obtain RM8 8.92g (yield: the 61%th, proterties: white crystal).

¹H-NMR(400MHz)in CDCl3:2.02-1.87ppm(m,8H),2.67-2.60ppm(m,2H),3.15- 3.08ppm(m,2H),4.13-4.02ppm(m,4H),4.65-4.60ppm(m,2H),5.66ppm(s,2H),6.25ppm(d,J =2.4Hz, 2H), 6.94ppm (d, J=8.8Hz, 2H), 6.99ppm (t, J=8.6Hz, 1H) 7.28-7.22ppm (m, 2H), 7.44ppm (d, J=8.8Hz, 2H).

In the 300mL four-neck flask possessing magnetic stirring apparatus, 50.0g DMF puts into 4,4 '-xenol 20.0g (107mmol) with potassium carbonate 44.6g (3.0eq), KI 1.82g (0.1eq), being heated to 100 DEG C, DMF 10.0g is used in dropping 2-bromomethyl-DOX the 39.8g (2.2eq) of dilution, stirs 6 hours at the same temperature.After 6 hours, further Add 2-bromomethyl-DOX 5.38g (0.3eq), stir 18 hours.After reaction terminates, reactant liquor is added extremely pure Water 400g and make crystal separate out, carry out filtering and filtrate MeOH 60.0g being carried out pulp cleaning, again filter and obtain White solid.Make gained white solid be suspended in THF 500g, add activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 1.00g, after 60 DEG C of stirrings 30 minutes, filters (45 DEG C) while hot.Cooling filtrate, result Separate out white crystal, therefore, obtained RM9-A 13.0g (yield: the 34%th, proterties: white solid) by filtration drying.

¹H-NMR(400MHz)in DMSO-d6:3.85-3.93ppm(m,4H),3.95-3.99ppm(m,4H), 4.03ppm (d, J=4.0Hz, 4H), 5.21ppm (t, J=4.0Hz, 2H), 7.01ppm (d, J=8.8Hz, 4H), 7.53ppm (d, J=8.4Hz, 4H).

In the 300mL four-neck flask possessing magnetic stirring apparatus, 99.5g THF puts into compound obtained above (RM9-A) 9.95g (27.8mmol), 2-(bromomethyl) ethyl acrylate 11.8g (2.2eq), stannic chloride 12.6g (2.4eq), 10wt% aqueous hydrochloric acid solution 34.8g, stirs 1.5 hours with 60 DEG C.After 1.5 hour, 20wt% aqueous hydrochloric acid solution 9.95g is added After, stir 21 hours further, make reaction terminate.Thereafter, THF is removed in decompression distillation, adds ethyl acetate 199g, removes water Phase.Then, organic layer pure water 59.7g is cleaned 2 times.Reclaim organic phase, after ethyl acetate is removed in decompression distillation, add THF 149g carries out return stirring.Then, add activated carbon (trade mark: special egression dry product Japan EnviroChemicals, Ltd. system) 0.48g stirring 1 hour, after carrying out processed with magnesium sulfate, is filtered, obtains uniform filtrate.Then, Being carried out reduced pressure concentration and making THF amount be 79.6g, after adding MeOH 159g with 55 DEG C, ice-cold stirring is a little while.Will thus The crystal separating out carries out filtration drying, thus obtains RM9 8.4g (yield: 74%, proterties: white crystal).

¹H-NMR(400MHz)in DMSO-d6:2.82-2.89ppm(m,2H),3.10-3.18ppm(m,2H), 4.14ppm (dd, J=5.4Hz, J=11.0Hz, 2H), 4.25ppm (dd, J=2.6Hz, J=11.0Hz, 2H), 5.78- 5.79ppm (m, 2H), 6.10-6.08ppm (m, 2H), 7.00ppm (d, J=8.4Hz, 4H), 7.55ppm (d, J=8.4Hz).

In the 200mL four-neck flask possessing magnetic stirring apparatus, 20.0g NMP puts into 4,4 '-xenol 10.0g (53.7mmol), 4-chlorobutyraldehyde dimethylacetal 18.4g (2.2eq), potassium carbonate 22.3g (3.0eq), KI 1.78g (0.2eq), stir 3 hours with 80 DEG C.Thereafter, add 4-chlorobutyraldehyde dimethylacetal 2.45g (0.3eq), stir 16 further little When.After reaction, reactant liquor is diluted by ethyl acetate 50.0g, after filtering inorganic salt, filtrate is diluted by ethyl acetate 50.0g, Pure water 50.0g is used to clean at 50 DEG C 3 times.Thereafter, this organic phase with sodium sulfate is carried out processed, be evaporated to Till gross weight reaches 68.0g, filter separated out crystal.Add THF 5.0g and MeOH 20.0g in crude product, with 50 After DEG C making it dissolve, cooling is simultaneously stirred a little while.Carry out filtration drying to the crystal separating out, thus obtain RM10-A15.8g and (receive Rate: the 70%th, proterties: white solid).

¹H-NMR(400MHz)in DMSO-d6:1.66-1.75ppm(m,8H),3.24ppm(s,12H),4.00ppm(t, J=6.2Hz, 4H), 4.42ppm (t, J=5.2Hz, 2H), 6.97ppm (d, J=8.8Hz, 4H), 7.52ppm (d, J= 8.4Hz,4H).

In the 500mL four-neck flask possessing magnetic stirring apparatus, 56.4g THF puts into compound obtained above (RM10-A) 14.8g (35.4mmol), 2-(bromomethyl) ethyl acrylate 15.0g (2.2eq), stannic chloride 16.1g (2.4eq), BHT 0.39g (5mol%), 20wt%HCl aqueous solution 51.8g, stir 3 hours with 60 DEG C.After reaction, Carry out reduced pressure concentration to reactant liquor, after adding pure water 148g, filter separated out crystal, clean 2 times with pure water 148g.Then, Add THF 118g and MeOH 118g in this crystal, after making it dissolve at 50 DEG C, be cooled to room temperature and stir a little while. By filtering thus obtained crystal, thus obtain crude product.And then, in this crude product add THF 237g and IPA 237g, after making it dissolve, is cooled to room temperature and stirs a little while at 60 DEG C.The crystal thus separating out is filtered, After cleaning 3 times with THF 74.0g, carry out drying under reduced pressure, thus obtain RM107.20g (yield: the 44%th, proterties: white crystal).

¹H-NMR(400MHz)in DMSO-d6:1.75-1.85ppm(m,8H),2.60-2.68ppm(m,2H),3.08- 3.15ppm (m, 2H), 4.03ppm (t, J=5.2Hz, 4H), 4.61-4.67ppm (m, 2H) 5.72-5.73ppm (m, 2H), 6.04-6.05ppm (m, 2H), 6.98ppm (d, J=8.8Hz, 4H), 7.52ppm (d, J=8.8Hz, 4H).

By BODA (2.00g, 8.0mmol), DA-2 (2.40g, 6.0mmol), DA-4 (0.94g, 6.2mmol), DA-6 (1.77g, 3.8mmol), DA-8 (1.32g, 4.0mmol) dissolve in NMP (32.2g), after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (10.7g), at room temperature reacts 10 hours, thus obtains polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (5.7g) and pyridine (2.9g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-1.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 12000th, weight average molecular weight is 33000.

Add NMP (44.0g) in gained polyimide powder (A)-1 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D1.

By BODA (2.00g, 8.0mmol), DA-8 (3.30g, 10.0mmol), DA-2 (4.00g, 10.0mmol) at NMP (34.8g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (11.6g), at room temperature React 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (5.3g) and pyridine (2.7g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-2.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 15000th, weight average molecular weight is 41000.

Add NMP (44.0g) in gained polyimide powder (A)-2 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D2.

By BODA (2.00g, 8.0mmol), DA-6 (4.67g, 10.0mmol), DA-2 (4.00g, 10.0mmol) at NMP (38.9g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (13.0g), at room temperature React 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (3.1g) and pyridine (12.1g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), Leaching gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-3.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 15000th, weight average molecular weight is 36000.

Add NMP (44.0g) in gained polyimide powder (A)-3 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D3.

By BODA (2.00g, 8.0mmol), DA-7 (2.64g, 10.0mmol), DA-2 (4.00g, 10.0mmol) at NMP (32.8g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (10.9g), at room temperature React 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (3.7g) and pyridine (14.4g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), Leaching gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-4.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 25000th, weight average molecular weight is 45000.

Add NMP (44.0g) in gained polyimide powder (A)-4 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D4.

By TCA (1.35g, 6.0mmol), DA-1 (2.28g, 6.0mmol), DA-8 (2.97g, 9.0mmol) at NMP (24.9g) dissolve in, after 80 DEG C of reactions 3 hours, add CBDA (1.74g, 8.9mmol) and NMP (8.3g), at room temperature instead Answer 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (36g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (4.0g) and pyridine (2.1g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-5.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 20000th, weight average molecular weight is 43000.

Add NMP (44.0g) in gained polyimide powder (A)-5 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D5.

By BODA (2.00g, 8.0mmol), DA-8 (4.63g, 14.0mmol), DA-3 (2.61g, 6.0mmol) at NMP (34.5g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (11.5g), at room temperature React 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (5.3g) and pyridine (2.7g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-6.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 17000th, weight average molecular weight is 35000.

Add NMP (44.0g) in gained polyimide powder (A)-6 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D6.

By BODA (1.30g, 5.2mmol), DA-9 (2.09g, 3.9mmol), DA-8 (3.00g, 9.1mmol) at NMP (23.5g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (1.43g, 7.3mmol) and NMP (7.8g), at room temperature instead Answer 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (36g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (3.6g) and pyridine (1.9g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-7.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 16000th, weight average molecular weight is 36000.

Add NMP (44.0g) in gained polyimide powder (A)-7 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D7.

By BODA (2.00g, 8.0mmol), DA-8 (3.96g, 12.0mmol), DA-1 (3.04g, 8.0mmol) at NMP (33.9g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (11.3g), at room temperature React 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (5.4g) and pyridine (2.8g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-8.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 18000th, weight average molecular weight is 40000.

Add NMP (44.0g) in gained polyimide powder (A)-8 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D8.

By BODA (2.00g, 8.0mmol), DA-1 (2.28g, 6.0mmol), DA-4 (1.22g, 8.0mmol), DA-5 (1.45g, 6.0mmol) dissolves in NMP (29.5g), after 60 DEG C of reactions 3 hours, and PMDA (2.53g, 11.6mmol) and NMP (9.5g), at room temperature react 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (6.4g) and pyridine (3.3g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-9.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 10000th, weight average molecular weight is 31000.

Add NMP (44.0g) in gained polyimide powder (A)-9 (6.0g), make it molten with 50 DEG C of stirrings 5 hours Solve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 little When and obtain aligning agent for liquid crystal D9.

Relative to the aligning agent for liquid crystal D8 7.0g obtaining in synthesis example 18, add the liquid crystal aligning obtaining in synthesis example 19 Agent D9 3.0g, being stirred at room temperature 5 hours, thus obtains aligning agent for liquid crystal D10.

By BODA (2.00g, 8.0mmol), DA-1 (1.52g, 4.0mmol), DA-4 (1.22g, 8.0mmol), DA-8 (2.64g, 8.0mmol) dissolves in NMP (20.7g), after 60 DEG C of reactions 3 hours, and PMDA (2.53g, 11.6mmol) and NMP (9.9g), at room temperature react 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (6.1g) and pyridine (3.2g), react 3 hours with 50 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-10.The acid imide rate of this polyimides is 60%, and number-average molecular weight is that the 9000th, weight average molecular weight is 25000.

Add NMP (44.0g) in gained polyimide powder (A)-10 (6.0g), make it with 50 DEG C of stirrings 5 hours Dissolve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 Hour and obtain aligning agent for liquid crystal D11.

Relative to the aligning agent for liquid crystal D8 7.0g obtaining in synthesis example 18, add the liquid crystal aligning obtaining in synthesis example 21 Agent D11 3.0g, is stirred at room temperature 5 hours, thus obtains aligning agent for liquid crystal D12.

By BODA (3.75g, 15.0mmol), DA-1 (3.81g, 10.0mmol), DA-4 (1.52g, 10.0mmol) at NMP (30.0g) dissolve in, after 80 DEG C of reactions 5 hours, add CBDA (0.94g, 4.8mmol) and NMP (10.0g), anti-with 40 DEG C Answer 10 hours, thus obtain polyamic acid solution.

After this polyamic acid solution (50g) middle interpolation NMP is diluted to 6 mass %, as imidization catalyst Add acetic anhydride (4.7g) and pyridine (3.7g), react 3 hours with 80 DEG C.Put into this reaction solution to methyl alcohol (700ml), filter Take gained sediment.This sediment methyl alcohol is cleaned, carries out drying under reduced pressure with 100 DEG C, thus obtain polyimide powder (A)-11.The acid imide rate of this polyimides is 55%, and number-average molecular weight is that the 20000th, weight average molecular weight is 40000.

Add NMP (44.0g) in gained polyimide powder (A)-11 (6.0g), make it with 50 DEG C of stirrings 5 hours Dissolve.Add 3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) in this solution, be stirred at room temperature 5 Hour and obtain aligning agent for liquid crystal D13.

By BODA (2.00g, 8.0mmol), DA-6 (6.53g, 14.0mmol), DA-2 (2.40g, 6.0mmol) at NMP (26.4g) dissolve in, after 60 DEG C of reactions 3 hours, add CBDA (2.27g, 11.6mmol) and NMP (13.2g), at room temperature React 10 hours, thus obtain polyamic acid solution.The number-average molecular weight of this polyamic acid solution is the 20000th, weight average molecular weight It is 40000.

Add NMP (40.0g), BCS (30.0g) in this polyamic acid solution (30g), be stirred at room temperature 5 hours and Obtain aligning agent for liquid crystal D14.

In the 300ml four-neck flask possessing magnetic stirring apparatus, 18.1g NMP puts into RM1-A 9.0g (44.1mmol), after, being washed altogether by NMP 17.9g, add potassium carbonate 18.3g (3.0eq), washed altogether by NMP18.0g.One While be stirred them at 80 DEG C, expend 30 minutes dropping 2-(2-bromoethyl)-DOX 17.6g (2.2eq), after, stir 18 hours.After 18 hours, add 2-(2-bromoethyl)-DOX 2.4g (0.3eq) further, And then make it react 3.5 hours, confirm that intermediate disappears.After reaction terminates, in reactant liquor, at room temperature add substantial amounts of water, Dissolve potassium carbonate while making the crystal of object separate out, and filter.The crystal pure water of recovery is carried out 2 pulps Clean, carry out filtration drying, thus obtain the crude product 17.8g (yield: the 100%th, proterties: filbert crystal) of RM11-A.

¹H-NMR(400MHz)in DMSO-d₆: 7.57ppm (d, J=8.8Hz, 2H), 7.49ppm (dd, J=2.2Hz, J =13.0Hz, 1H), 7.38ppm (d, J=10.0Hz, 1H), 7.21ppm (t, J=8.8Hz, 1H), 6.99ppm (d, J= 8.4Hz, 2H), 5.02-4.99ppm (m, 2H), 4.18ppm (t, J=6.6Hz, 2H), 4.10ppm (t, J=6.6Hz, 2H), 3.94-3.91ppm(m,4H),3.82-3.78ppm(m,4H),2.09-2.02ppm(m,4H).

In the 500ml four-neck flask possessing magnetic stirring apparatus, in 135g THF, put into RM11-A15.0g (37.1mmol), after stannic chloride (II) anhydride 16.9g (2.4eq), 2-(bromomethyl) ethyl acrylate 15.9g (2.2eq), 45 minutes dropping 10wt%HCl aqueous solution 52.5g are expended at 20～30 DEG C.Thereafter, be stirred at room temperature 7 days, make raw material and in Mesosome disappears.Then, it is divided into two-phase by adding toluene 300g in reactant liquor, remove desalination by separatory while hot (50 DEG C) Acid phase.Temporarily organic phase is recycled to flask, at 50 DEG C, in the removable flask of the jacketed of stirring, drips 6wt% KOH aqueous solution 300g.During interface produce insoluble matter, therefore add 6wt%KOH aqueous solution 150g.Then, alkali phase is removed After, after organic phase is cleaned 3 times with pure water 300g, reclaim organic phase.It is added to activated carbon 0.75g (trade mark: special egression Dry product Japan EnviroChemicals, Ltd. system), sodium sulphate 30.0g, THF 105g, be stirred at room temperature 30 minutes After, carry out separation of solid and liquid, reclaim filtrate.Carried out concentrating solid, after adding MeOH 45.0g, at room temperature carried out 1 hour Pulp clean.After filtering, after gained filtrate MeOH 7.5g is carried out, carry out drying under reduced pressure, thus Obtain RM11 7.6g (yield: the 45%th, proterties: white crystal).

¹H-NMR(400MHz)in DMSO-d₆: 7.59ppm (d, J=8.8Hz, 2H), 7.51ppm (dd, J=2.0Hz, J =12.8Hz, 1H), 7.40ppm (dd, J=1.6Hz, J=8.0Hz, 1H), 7.34ppm (t, J=9.0Hz, 1H), 7.01ppm (d, J=8.8Hz, 2H), 6.05ppm (dd, J=2.6Hz, J=5.0Hz, 2H), 5.74ppm (d, J=2.0Hz, 2H), 4.81- 4.75ppm (m, 2H), 4.20ppm (t, J=6.2Hz, 2H), 4.13ppm (t, J=6.2Hz, 2H), 3.21-3.12ppm (m, 2H),2.79-2.71ppm(m,2H),2.17-2.08ppm(m,4H).

[embodiment 1]

Relative to the aligning agent for liquid crystal D1 10.0g obtaining in synthesis example 11, add the polymerism obtaining in synthesis example 1 Compound RM1 0.06g (being 10 mass % relative to solid constituent), is stirred at room temperature 3 hours and makes it dissolve, thus prepare Aligning agent for liquid crystal D15.

Gained aligning agent for liquid crystal D15 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 2]

In embodiment 1, by the quantitative change more 0.09g (being 15 mass % relative to solid constituent) of polymerizable compound RM1, In addition, utilize method same as in Example 1, prepare aligning agent for liquid crystal D16.

Gained aligning agent for liquid crystal D16 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 3]

In embodiment 1, except using the polymerizable compound RM2 obtaining in synthesis example 2 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D17.

Gained aligning agent for liquid crystal D17 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 4]

In embodiment 2, except using the polymerizable compound RM2 obtaining in synthesis example 2 to replace polymerizable compound RM1 Outside, utilize method same as in Example 2, prepare aligning agent for liquid crystal D18.

Gained aligning agent for liquid crystal D18 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 5]

In embodiment 1, except using the polymerizable compound RM3 obtaining in synthesis example 3 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D19.

Gained aligning agent for liquid crystal D19 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 6]

In embodiment 2, except using the polymerizable compound RM3 obtaining in synthesis example 3 to replace polymerizable compound RM1 Outside, utilize method same as in Example 2, prepare aligning agent for liquid crystal D20.

Gained aligning agent for liquid crystal D20 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 7]

In embodiment 1, except using the polymerizable compound RM4 obtaining in synthesis example 4 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D21.

Gained aligning agent for liquid crystal D21 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 8]

In embodiment 2, except using the polymerizable compound RM4 obtaining in synthesis example 4 to replace polymerizable compound RM1 Outside, utilize method same as in Example 2, prepare aligning agent for liquid crystal D22.

Gained aligning agent for liquid crystal D22 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 9]

In embodiment 1, in addition to using the aligning agent for liquid crystal D2 obtaining in synthesis example 12 to replace aligning agent for liquid crystal D1, Utilize method same as in Example 2, prepare aligning agent for liquid crystal D23.

Gained aligning agent for liquid crystal D23 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 10]

In embodiment 1, in addition to using the aligning agent for liquid crystal D3 obtaining in synthesis example 13 to replace aligning agent for liquid crystal D1, Utilize method same as in Example 2, prepare aligning agent for liquid crystal D24.

Gained aligning agent for liquid crystal D24 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 11]

In embodiment 1, in addition to using the aligning agent for liquid crystal D4 obtaining in synthesis example 14 to replace aligning agent for liquid crystal D1, Utilize method same as in Example 2, prepare aligning agent for liquid crystal D25.

Gained aligning agent for liquid crystal D25 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 12]

In embodiment 1, in addition to using the aligning agent for liquid crystal D5 obtaining in synthesis example 15 to replace aligning agent for liquid crystal D1, Utilize method same as in Example 2, prepare aligning agent for liquid crystal D26.

Gained aligning agent for liquid crystal D26 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 13]

In embodiment 1, in addition to using the aligning agent for liquid crystal D6 obtaining in synthesis example 16 to replace aligning agent for liquid crystal D1, Utilize method same as in Example 2, prepare aligning agent for liquid crystal D27.

Gained aligning agent for liquid crystal D27 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 14]

In embodiment 1, in addition to using the aligning agent for liquid crystal D7 obtaining in synthesis example 17 to replace aligning agent for liquid crystal D1, Utilize method same as in Example 2, prepare aligning agent for liquid crystal D28.

Gained aligning agent for liquid crystal D28 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 15]

In embodiment 1, except use in synthesis example 20 the aligning agent for liquid crystal D10 obtaining replace aligning agent for liquid crystal D1 it Outward, utilize method same as in Example 2, prepare aligning agent for liquid crystal D29.

Gained aligning agent for liquid crystal D29 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 16]

In embodiment 1, except use in synthesis example 22 the aligning agent for liquid crystal D12 obtaining replace aligning agent for liquid crystal D1 it Outward, utilize method same as in Example 2, prepare aligning agent for liquid crystal D30.

Gained aligning agent for liquid crystal D30 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 17]

In embodiment 1, except use in synthesis example 23 the aligning agent for liquid crystal D13 obtaining replace aligning agent for liquid crystal D1 it Outward, utilize method same as in Example 2, prepare aligning agent for liquid crystal D31.

Gained aligning agent for liquid crystal D31 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 18]

In embodiment 1, except use in synthesis example 24 the aligning agent for liquid crystal D14 obtaining replace aligning agent for liquid crystal D1 it Outward, utilize method same as in Example 2, prepare aligning agent for liquid crystal D32.

Gained aligning agent for liquid crystal D32 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 19]

In embodiment 1, except using the polymerizable compound RM7 obtaining in synthesis example 7 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D33.

Gained aligning agent for liquid crystal D33 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 20]

In embodiment 1, except using the polymerizable compound RM8 obtaining in synthesis example 8 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D34.

Gained aligning agent for liquid crystal D34 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

(comparative example 1)

In embodiment 1, except using the polymerizable compound RM5 obtaining in synthesis example 5 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D35.

Gained aligning agent for liquid crystal D35 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

(comparative example 2)

In embodiment 2, except using the polymerizable compound RM5 obtaining in synthesis example 5 to replace polymerizable compound RM1 Outside, utilize method same as in Example 2, prepare aligning agent for liquid crystal D36.

Gained aligning agent for liquid crystal D36 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Confirm precipitate.

(comparative example 3)

In embodiment 1, except using the polymerizable compound RM6 obtaining in synthesis example 6 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D37.

Gained aligning agent for liquid crystal D37 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Confirm precipitate.

(comparative example 4)

In embodiment 2, except using the polymerizable compound RM6 obtaining in synthesis example 6 to replace polymerizable compound RM1 Outside, utilize method same as in Example 2, prepare aligning agent for liquid crystal D38.

Gained aligning agent for liquid crystal D38 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Confirm precipitate.

(comparative example 5)

In embodiment 1, except using the polymerizable compound RM9 obtaining in synthesis example 9 to replace polymerizable compound RM1 Outside, utilize method same as in Example 1, prepare aligning agent for liquid crystal D39.

Gained aligning agent for liquid crystal D39 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

(comparative example 6)

In embodiment 1, except using the polymerizable compound RM10 obtaining in synthesis example 10 to replace polymerizable compound Outside RM1, utilize method same as in Example 1, prepare aligning agent for liquid crystal D40.

Gained aligning agent for liquid crystal D40 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

[embodiment 21]

Use in embodiment 1 the aligning agent for liquid crystal D15 obtaining, according to the step as shown in following, carry out SC-PVA side The making of the liquid crystal cells of formula.

The aligning agent for liquid crystal D15 obtaining in embodiment 1 is spun on Pixel Dimensions be 100 μ m 300 μm and formed wired/ Space is respectively the ito surface of the ITO electrode substrate of the ITO electrode pattern of 5 μm, after the press drying 90 seconds of 80 DEG C, with 200 DEG C heated air circulation type baking oven carry out 30 minutes burn till, thus form the liquid crystal orientation film of thickness 100nm.

In addition, aligning agent for liquid crystal D1 is spun on the ito surface not forming electrode pattern, with the press drying 90 seconds of 80 DEG C After, carry out 30 minutes burn till with the heated air circulation type baking oven of 200 DEG C, thus form the liquid crystal orientation film of thickness 100nm.

For above-mentioned two substrate, after the liquid crystal orientation film of a substrate spreads the pearl sept of 4 μm, by it Printing and sealing agent (solvent type heat-curing type epoxy resin).Then, it is formed with liquid crystal orientation film side with another substrate Surface is as inner side, after pasting with substrate before, makes sealant cures make dummy cell.Inject normal direction by decompression This dummy cell injects liquid crystal MLC-6608 (MERCK CORPORATION system, trade name), thus makes liquid crystal cells.Thereafter, The liquid crystal cells making is placed 1 hour at the heated air circulation type baking oven of 120 DEG C, carries out the reorientation process of liquid crystal.

It is measured by the response speed to gained liquid crystal cells for the following method.Thereafter, this liquid crystal cells is being applied In the state of 15V D/C voltage, irradiate 10J/cm from the outside of this liquid crystal cells²The UV of bandpass filter passing through 365nm. Thereafter, again measure response speed, the response speed after UV pre-irradiation is contrasted.

In addition, the unit after irradiating for UV, measure the tilt angle of pixel portion.

And then, the unit not irradiating UV is placed one day, thereafter, carries out the polarized light microscope observing of liquid crystal cells.Can To think: when dissolubility in liquid crystal for the polymerizable compound is low, also easily separate out in liquid crystal cells, produce bright spot.Will knot Fruit is shown in table 2.

First, it is being made up of backlight, one group of polarizer, light quantity detector being set to Nicol crossed state successively In determinator, between one group of polarizer, configure liquid crystal cells.Now, make formation wired/the pattern phase of the ITO electrode in space Nicol crossed is reached to the angle of 45 °.Further, voltage ± 6V, the square of frequency 1kHz are applied to above-mentioned liquid crystal cells Shape ripple, with oscillograph read utilize light quantity detector to observe brightness reach saturated till change, during by no applied voltage Brightness be set to 0%, by applying ± 4V voltage, the value of luminance saturation is set to 100%, and from 10%, brightness is changed to 90% is The time only expended is as response speed.

Employ the LCD analyzer LCA-LUV42A that Meiryo Technica Corporation manufactures.

(embodiment 22～40)

In addition to the aligning agent for liquid crystal described in use table 1 replaces aligning agent for liquid crystal D15, carry out identical with embodiment 21 Operation, the response speed after UV pre-irradiation is contrasted.In addition, also carry out in the mensuration of tilt angle and liquid crystal cells is bright Point is observed.

It should be noted that embodiment is the 23rd, the 24th, the 27th, in 28, the heated air circulation type baking oven of 140 DEG C is used to replace 200 DEG C Heated air circulation type baking oven.

(embodiment 41)

Relative to the aligning agent for liquid crystal D8 (7.0g) obtaining in synthesis example 18, add the liquid crystal aligning obtaining in synthesis example 19 Agent D9 (3.0g), is stirred at room temperature 5 hours, thus prepares aligning agent for liquid crystal D1010.0g.To this aligning agent for liquid crystal D10 (10.0g) (solid constituent relative to aligning agent for liquid crystal D10 is 10 matter to add the RM11 0.06g being synthesized by synthesis example 25 in Amount %), it is stirred at room temperature 3 hours and makes it dissolve, thus prepare aligning agent for liquid crystal D41.

Gained aligning agent for liquid crystal D41 is preserved in the freezer of-20 DEG C 1 day, when at room temperature placing 3 hours and thaw, Unconfirmed to precipitate.

(embodiment 42)

For the aligning agent for liquid crystal D41 of preparation in embodiment 41, carry out the operation identical with embodiment 21, by UV pre-irradiation After response speed contrast.In addition, the bright spot carrying out in the mensuration of tilt angle and liquid crystal cells is observed.

(comparative example 7～12)

In addition to using aligning agent for liquid crystal D35～D40 to replace aligning agent for liquid crystal D15 respectively, carry out and embodiment 21 Response speed after UV pre-irradiation is contrasted by identical operation.In addition, also carry out in mensuration and the liquid crystal cells of tilt angle Bright spot observe.

[table 2]

Table 2. embodiment 21～40 and 42 and comparative example 7～12

When embodiment 21 and 22 is contrasted with comparative example 7 and 8, especially embodiment 22 and comparative example 8 are carried out right Than when understand: in the case of having identical skeleton, (difference of RM1 and RM5 is, there is fluorine replacement (RM1)/there is not fluorine Replace (RM5)), make its dissolubility in varnish improve by importing halogen group.In addition, bright according in liquid crystal cells Point is observed and is understood: dissolubility in liquid crystal for the polymerizable compound also improves.

For identical viewpoint, by embodiment 39, (difference of RM7 and RM9 is, there is fluorine and replaces with comparative example 11 (RM7)/there is not fluorine and replace (RM9)), (difference of RM8 and RM10 is embodiment 40 and comparative example 12, there is fluorine replacement (RM8)/there is not fluorine and replace (RM10)) when contrasting, observe according to the bright spot in liquid crystal cells and understand: polymerizable compound Dissolubility in liquid crystal improves.

Even if in addition, can be confirmed that there is upright and outspoken compared with biphenyl backbone and dissolubility according to embodiment 25 and embodiment 26 Low terphenyl skeleton, makes dissolubility in aligning agent for liquid crystal for the polymerizable compound improve also by importing halogen group, The storage stability of aligning agent for liquid crystal also improves.

Similarly, the 23rd, the 24th, the 27th, 28 Gao Rong in aligning agent for liquid crystal for the polymerizable compound is also confirmed according to embodiment Xie Xing.

Thus, understand with regard to the polymerizable compound being optionally substituted by halogen: molten in aligning agent for liquid crystal of polymerizable compound Solution property improves, and aligning agent for liquid crystal shows high storage stability, and then, the dissolubility in liquid crystal also improves.

And then confirm: it is added with the aligning agent for liquid crystal of the polymerizable compound being optionally substituted by halogen for SC-PVA mode For liquid crystal cells, show inclination angle in the same manner as being added with the aligning agent for liquid crystal of the polymerizable compound not being optionally substituted by halogen.

Claims

1. an aligning agent for liquid crystal, it contains:

[I] at least a kind of polymerizable compound in the group being made up of the compound shown in following formula I-1～I-3；And

[II] is selected from least a kind of polymer in polyimide precursor and polyimides,

In Formulas I-1～I-3, Ar₁～Ar₃It is each independently the divalence of the aromatic ring comprising to have at least 1 halogenic substituent Organic group, n₁、n₂And n₆Represent the integer of 0～6, n independently of one another₃、n₄And n₅Represent the integer of 1～6, R independently of one another₁ ～R₃Represent the straight chained alkyl of hydrogen or carbon number 1～4 or the branched alkyl of carbon number 1～4 independently of one another.

2. aligning agent for liquid crystal according to claim 1, wherein, described Ar₁～Ar₃It is each independently selected from by following formula Divalent group in the group of IB-1～IB-3 composition,

In Formulas I B-1～IB-3, X represents halogen group, m₁～m₈It is each independently integer, m₁+m₂It is more than 1 and less than 8, m₃+ m₄+m₅It is more than 1 and less than 10, m₆+m₇+m₈It is more than 1 and less than 12.

3. aligning agent for liquid crystal according to claim 2, wherein, the group shown in described Formulas I B-1 is following formula IB-1a institute The group showing, the group shown in described Formulas I B-2 is the group shown in following formula IB-2a, under the group shown in described Formulas I B-3 is State the group shown in Formulas I B-3a,

4. the aligning agent for liquid crystal according to according to any one of claims 1 to 3, wherein, described [II] polymer has (I) makes liquid Brilliant vertical orientated side chain.

5. aligning agent for liquid crystal according to claim 4, wherein, described [II] polymer also has (II) photoreactive side Chain.

6. a liquid crystal orientation film, it is the aligning agent for liquid crystal having according to any one of Claims 1 to 5 and is formed.

7. liquid crystal represents an element, and it has the liquid crystal orientation film described in claim 6.